4-(3,3-dihalo-allyloxy) phenol derivatives having pesticidal properties

ABSTRACT

Compounds of formula (I) wherein A o  is a bond or a C 1 -C 6 alkylene bridge; A 1 , A 2  and A 3  are a C 1 -C 6 alkylene bridge; D is CH or N; W is, for example, O, S, SO, S0 2 , —C(═O)—O— or —O—C(═O)—; T is a bond or, for example, O, NH, S, SO or SR 2 ; Q is, for example, O, S, SO or SO 2 ; Y is, for example, O, S, SO or SO 2 ; X 1  and X 2  are each independently of the other fluorine, chlorine or bromine; R 1 , R 2  and R 3  are, for example, H, halogen, OH, SH, CN or nitro; R 4  is, for example, H, halogen, OH, SH, CN, nitro or C 1 -C 6 alkyl; R 5  is, for example, H, CN, OH, C 1 -C 6 alkyl or C 3 -C 8 cycloalkyl; k is 1, 2 or 3 when D is nitrogen; or is 1, 2, 3 or 4 when D is CH; m is 1 or 2; E is heteroaryl which is unsubstituted or substituted—depending upon the substitutions possible on the ring—by from one to four identical or different substituents selected from R 10 ; and R 10  is, for example, halogen, CN, NO 2 , OH, SH or C 1 -C 6 alkyl; and, where applicable, their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in each case in free form or in salt form, a process for the preparation of those compounds and their use, pesticidal compositions in which the active ingredient has been selected from those compounds or an agrochemically acceptable salt thereof, a process for the preparation of those compositions and their use, plant propagation material treated with those compositions, and a method of controlling pests.

This application is a 371 of International Application No.PCT/EP2003/009636 filed Aug. 29, 2003, which claims priority to CH1487/02, filed Aug. 30, 2002, the contents of which are incorporatedherein by reference.

The present invention relates (1) to compounds of formula

wherein

A₀, A₁ and A₂ are each independently of the other a bond or aC₁-C₆alkylene bridge which is unsubstituted or substituted by from oneto six identical or different substituents selected fromC₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl and C₁-C₃haloalkyl;

A₃ is a C₁-C₆alkylene bridge which is unsubstituted or substituted byfrom one to six identical or different substituents selected fromC₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl and C₁-C₃haloalkyl;

D is CH or N;

X₁ and X₂ are each independently of the other fluorine, chlorine orbromine;

R₁, R₂ and R₃ are each independently of the others H, halogen, OH, SH,CN, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy,—S(═O)—C₁-C₆alkyl, —S(O)₂—C₁-C₆alkyl, C₁-C₆alkoxycarbonyl orC₃-C₆haloalkynyloxy; the substituents R₃ being independent of oneanother when m is 2;

R₄ is H, halogen, OH, SH, CN, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkylcarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy,C₂-C₆alkynyloxy, —S(═O)—C₁-C₆alkyl, —S(═O)₂—C₁-C₆alkyl orC₁-C₆alkoxycarbonyl; the substituents R₄ being independent of oneanother when k is greater than 1; or N(R₅)₂ wherein the two substituentsR₅ are independent of one another;

R₅ is H, CN, OH, C₁-C₆alkyl, C₃-C₈cycloalkyl,C₃-C₈cycloalkyl-C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy,—C(═O)R₈, —C(═S)R₈, phenyl, benzyl; or phenyl or benzyl each of which issubstituted in the aromatic ring by from one to five identical ordifferent substituents selected from the group consisting of halogen,C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy, halo-C₁-C₆-alkoxy, hydroxy,cyano and nitro;

or the two substituents R₅ together form a four- to eight-membered,straight-chain or branched alkylene bridge wherein a CH₂ group may havebeen replaced by O, S or NR₉, and the alkylene bridge is unsubstitutedor substituted by from one to four identical or different substituentsselected from C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl andC₁-C₃haloalkyl;

W is O, NR₆, S, SO, SO₂, —C(═O)—O—, —O—C(═O)—, —C(═O)—NR₇— or—NR₇—C(═O)—;

T is a bond, O, NH, NR₆, S, SO, SO₂, —C(═O)—O—, —O—C(═O)—, —C(═O)—NR₇—or —NR₇—C(═O)—;

Q is O, NR₆, S, SO or SO₂;

Y is O, NR₆, S, SO or SO₂;

R₆ and R₇ are independently of each other H, C₁-C₆alkyl, C₁-C₃haloalkyl,C₁-C₆alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxyalkyl,C₃-C₈cycloalkyl or benzyl;

R₈ is C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy, C₃-C₆cycloalkyl, phenyl, benzyl;or phenyl or benzyl each of which is unsubstituted or substituted byfrom one to three identical or different substituents selected fromhalogen, CN, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₁-C₆alkoxyoarbonyl, C₁-C₃haloalkoxycarbonyl andC₂-C₆haloalkenyloxy;

R₉ is H, C₁-C₆alkyl, C₁-C₃haloalkyl, C₁-C₆-alkylcarbonyl,C₁-C₆haloalkylcarbonyl, C₁-C₆alkoxyalkyl, C₃-C₈cycloalkyl or benzyl;

k is 1, 2 or 3 when D is nitrogen; or is 1, 2, 3 or 4 when D is CH;

m is 1 or 2;

E is heteroaryl which is unsubstituted or substituted—depending upon thesubstitutions possible on the ring—by from one to four identical ordifferent substituents selected from R₁₀;

R₁₀ is halogen, CN, NO₂, OH, SH, C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆hydroxyalkyl, C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆haloalkynyl,C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆haloalkoxy,C₁-C₆haloalkoxy-C₁-C₆alkyl, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy,C₂-C₆alkenyloxy-C₁-C₆alkyl, C₂-C₆haloalkenyloxy-C₁-C₆alkyl,C₃-C₆alkynyloxy, C₃-C₆haloalkynyloxy, C₃-C₆alkynyloxy-C₁-C₆alkyl,C₃-C₈cycloalkoxy, C₃-C₈cycloalkyl-C₁-C₆alkoxy,C₃-C₈cycloalkoxy-C₁-C₆alkyl, C₃-C₈cycloalkoxy-C₁-C₆alkoxy,C₃-C₈cycloalkyl-C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylcarbonyl-C₁-C₆alkyl,C₁-C₆alkoxycarbonyl-C₁-C₆alkyl, C₁-C₆alkylthio, C₂-C₆alkenylthio,C₃-C₆alkynylthio, C₃-C₆cycloalkylthio, C₃-C₆cycloalkyl-C₁-C₆alkylthio,C₂-C₆haloalkenylthio, C₁-C₆haloalkylthio, NH₂, NH(C₁-C₆alkyl),N(C₁-C₆alkyl)₂, C₁-C₆alkylcarbonylamino, C₁-C₆haloalkylcarbonylamino,C₁-C₆alkoxycarbonylamino, C₁-C₆alkylaminocarbonylamino, —SO—C₁-C₆alkyl,—SO-halo-C₁-C₆alkyl, —SO₂—C₁-C₆alkyl, —SO₂-halo-C₁-C₆alkyl, —C(═O)R₁₁,phenyl or benzyl; wherein the phenyl and benzyl radicals may beunsubstituted or may carry independently of each other one to threesubstituents selected form the group consisting of halogen, OH, SH, CN,nitro, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy,—S(═O)—C₁-C₆alkyl, —S(O)₂—C₁-C₆alkyl, C₁-C₆alkoxycarbonyl andC₂-C₆haloalkenyloxy; and

R₁₁ is H, OH, C₁-C₆alkyl, C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-Cralkyl,C₁-C₆haloalkyl, C₁-C₆alkoxy, C₃-C₈cycloalkoxy,C₃-C₈cycloalkyl-C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyl,C₂-C₆haloalkynyl, C₂-C₆alkynyloxy, C₂-C₆haloalkynyloxy, NH₂,NH—C₁-C₆alkyl, —N(C₁-C₆alkyl)₂, NH-phenyl, NH-benzyl, phenoxy orbenzyloxy;

and, where applicable, their possible E/Z isomers, E/Z isomeric mixturesand/or tautomers, in each case in free form or in salt form, to aprocess for the preparation of those compounds, E/Z isomers andtautomers and to their use, to pesticidal compositions in which theactive ingredient has been selected from those compounds, E/Z isomersand tautomers, and to a process for the preparation of thosecompositions and to their use, to intermediates and, where applicable,their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, infree form or in salt form, for the preparation of those compounds, whereapplicable to tautomers, in free form or in salt form, of thoseintermediates and to a process for the preparation of thoseintermediates and their tautomers and to their use.

Certain dihaloallyl derivatives are proposed in the literature as activeingredients in pesticidal compositions. The biological properties ofthose known compounds are not entirely satisfactory in the field of pestcontrol, however, for which reason there is a need to provide furthercompounds having pesticidal properties, especially for controllinginsects and members of the order Acarina, that problem being solvedaccording to the invention by the provision of the present compounds offormula (I).

The compounds of formula (I) and, where applicable, their tautomers areable to form salts, e.g. acid addition salts. The latter are formed, forexample, with strong inorganic acids, such as mineral acids, e.g.sulfuric acid, a phosphoric acid or a hydrohalic acid, with strongorganic carboxylic acids, such as unsubstituted or substituted, e.g.halo-substituted, C₁-C₄alkanecarboxylic acids, for example acetic acid,saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic,maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g.ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, orwith organic sulfonic acids, such as unsubstituted or substituted, e.g.halo-substituted, C₁-C₄alkane- or aryl-sulfonic acids, e.g. methane- orp-toluene-sulfonic acid. Furthermore, compounds of formula (I) having atleast one acid group are able to form salts with bases. Suitable saltswith bases are, for example, metal salts, such as alkali metal oralkaline earth metal salts, e.g. sodium, potassium or magnesium salts,or salts with ammonia or an organic amine, such as morph-oline,piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g.ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- ortri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. Itmay also be possible for corresponding internal salts to be formed. Thefree form is preferred. Of the salts of compounds of formula (I),preference is given to agro-chemically advantageous salts. Hereinaboveand hereinbelow any reference to the free compounds of formula (I) or totheir salts is to be understood as including, where appropriate, alsothe corresponding salts or the free compounds of formula (I),respectively. The same applies to tautomers of compounds of formula (I)and their salts.

The general terms used hereinabove and hereinbelow have the meaningsgiven below, unless defined otherwise.

Halogen, as a group per se and as a structural element of other groupsand compounds, such as haloalkyl, halocycloalkyl, haloalkenyl,haloalkynyl and haloalkoxy, is fluorine, chlorine, bromine or iodine,especially fluorine, chlorine or bromine, more especially fluorine orchlorine, especially chlorine.

Unless defined otherwise, carbon-containing groups and compounds eachcontain from 1 up to and including 20, preferably from 1 up to andincluding 18, especially from 1 up to and including 10, more especiallyfrom 1 up to and including 6, especially from 1 up to and including 4,especially from 1 up to and including 3, more especially 1 or 2, carbonatoms; methyl is especially preferred.

Alkylene is a straight-chain or branched bridging member and isespecially —CH₂—, —CH₂CH₂—, —CH₂—CH₂—CH₂—, —CH₂—CH₂—CH₂—CH₂—,—CH₂—CH₂—CH₂—CH₂—CH₂—, —CH(CH₃)—, —CH₂(CH₃)CH₂—CH₂—, —CH(C₂H₅)—,—C(CH₃)₂—, —CH(CH₃)CH₂—, —CH(CH₃)CH(CH₃)— or —CH₂C(CH₃)₂—CH₂—.

Alkyl, as a group per se and as a structural element of other groups andcompounds, such as haloalkyl, alkoxy, alkoxyalkyl, haloalkoxy,alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulfonyl andalkylsulfonyloxy, is—in each case giving due consideration to the numberof carbon atoms contained in the group or compound in question—eitherstraight-chain, e.g. methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl,n-decyl, n-dodecyl, n-hexadecyl or n-octa-decyl, or branched, e.g.isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl orisohexyl.

Alkenyl and alkynyl—as groups per se and as structural elements of othergroups and compounds, such as haloalkenyl, haloalkynyl, alkenyloxy,haloalkenyloxy, alkynyloxy or halo-alkynyloxy—are straight-chain orbranched and each contains two or preferably one unsaturatedcarbon-carbon bond(s). There may be mentioned by way of example vinyl,prop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl,prop-2-yn-1-yl, but-2-yn-1-yl and but-3-yn-1-yl.

Cycloalkyl—as a group per se and as a structural element of other groupsand compounds, such as alkyl—is cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl or cyclooctyl. Cyclopentyl and cyclohexyl, andespecially cyclopropyl, are preferred.

Halo-substituted carbon-containing groups and compounds, such ashaloalkyl and haloalkoxy, may be partially halogenated orperhalogenated, the halogen substituents in the case of polyhalogenationbeing the same or different. Examples of haloalkyl—as a group per se andas a structural element of other groups and compounds, such ashaloalkoxy—are methyl substituted from one to three times by fluorine,chlorine and/or bromine, such as CHF₂, CF₃ or CH₂Cl; ethyl substitutedfrom one to five times by fluorine, chlorine and/or bromine, such asCH₂CF₃, CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CH₂CH₂Cl,CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl or isopropyl eachsubstituted from one to seven times by fluorine, chlorine and/orbromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃, CF₂CF₂CF₃, CH(CF₃)₂or CH₂CH₂CH₂Cl; and butyl or an isomer thereof substituted from one tonine times by fluorine, chorine and/or bromine, such as CF(CF₃)CHFCF₃,CF₂(CF₂)₂CF₃ or CH₂(CF₂)₂CF₃.

Aryl is especially phenyl or naphthyl, preferably phenyl.

Heteroaryl is to be understood as meaning a five- to seven-membered,especially a five-membered, monocyclic aromatic ring which contains fromone to four hetero atoms selected from the group consisting of N, O andS, especially N and S, or a bicyclic heteroaryl which may contain,either in one ring only—as in quinolinyl, quinoxalinyl, indolinyl,benzothiophenyl or benzofuranyl, for example—or in both rings—as inpteridinyl or purinyl, for example—one or more hetero atoms selectedindependently of one another from N, O and S. Preference is given topyridyl, pyrimidyl, pyrazinyl, pyridazinyl, s-triazinyl,1,2,4-triazinyl, thienyl, furanyl, pyranyl, pyrrolyl, pyrazolyl,imidazolyl, thiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl,isoxazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, benzothienyl,quinolinyl, quinoxalinyl, benzofuranyl, benzimidazolyl, benzpyrrolyl,benzthiazolyl, indolyl, coumarinyl, or indazolyl, which are preferablybonded via a carbon atom;

special preference is given to thienyl, pyrrolyl, pyrazolyl, imidazolyl,1,3-thiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-thiadiazolyl,1,2,4-thiadiazolyl, oxazolyl, isoxazolyl, 1,2,4-oxadiazolyl ortetrazolyl.

Preferred embodiments within the scope of the invention are

(2) compounds of formula (I) according to (1), wherein X₁ and X₂ arechlorine or bromine, especially chlorine;

(3) compounds of formula (I) according to (1) or (2), wherein the groupA₁-T-A₂ is a bond;

(4) compounds of formula (I) according to (1) to (3), wherein W isoxygen, —C(═O)O— or —C(═O)NH—, especially O;

(5) compounds of formula (I) according to (1) to (4), wherein A₃ is astraight-chain alkylene bridge, especially ethylene, propylene orbutylene, more especially propylene;

(6) compounds of formula (I) according to (1) to (5), wherein Q isoxygen;

(7) compounds of formula (I) according to (1) to (6), wherein Y isoxygen;

(8) compounds of formula (I) according to (1) to (7), wherein R₁ and R₂are bromine or chlorine, especially chlorine;

(9) compounds of formula (I) according to (1) to (8), wherein R₃ ishydrogen;

(10) compounds of formula (I) according to (1) to (9), wherein R₄ ishydrogen;

(11) compounds of formula (I) according to (1) to (10), wherein R₅ is H,C₁-C₆alkyl, C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy,C₂-C₆alkynyloxy;

(12) compounds of formula (I) according to (1) to (11), wherein R₆ is—C(═O)R₈ or —C(═S)R₈, and R₈ is C₁-C₆alkyl, C₁-C₆haloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy,C₃-C₆cycloalkyl or phenyl;

(13) compounds of formula (I) according to (1) or (2) and (4) to (11),wherein A₁ is a bond, T is oxygen and A₂ is a C₁-C₆alkylene bridge;

(14) compounds of formula (I) according to (1) or (2), wherein A₁ is abond, T is —C(═O)O— wherein the oxygen is bonded to A₂, or is —C(═O)NH—wherein NH is bonded to A₂, and A₂ is a C₁-C₆alkylene bridge;

(15) compounds of formula (I) according to (1) to (14), wherein E is afive- to seven-membered, monocyclic heteroaryl having from one to fourhetero atoms selected from the group consisting of N, O and S, orbicyclic heteroaryl which may contain, either in one ring only or inboth rings, one or more hetero atoms selected independently of oneanother from N, O and S, and which is unsubstituted or carries one ortwo substituents R₁₀, which are independent of each other; especiallywhich is unsubstituted or carries one substituent R₁₀;

especially five-membered monocyclic heteroaryl having from two to fourhetero atoms selected from the group consisting of N, O and S;

more especially five-membered monocyclic heteroaryl having one or twonitrogen atoms and one oxygen atom;

also more especially five-membered monocyclic heteroaryl having three orfour nitrogen atoms;

(16) compounds of formula (I) according to (1) to (15), wherein R₁₀ isH, CN, OH, NO₂, SH, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆-alkoxycarbonyl, C₁-C₆alkylthio,C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy, C₂-C₆-alkenylthio,C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl, cycloalkyl-C₁-C₆alkoxy orcycloalkyl-C₁-C₆alkylthio;

especially C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₁-C₆alkoxy,C₁-C₆alkylthio, C₂-C₆-alkenyloxy, C₂-C₆alkenylthio, C₃-C₈cycloalkyl,cycloalkyl-C₁-C₆alkoxy or cycloalkyl-C₁-C₆-alkylthio;

(17) compounds of formula (I) according to (1) to (15), wherein E istetrazol-1-yl which is unsubstituted or monosubstituted by C₁-C₆alkyl,C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆halo-alkenyl,C₃-C₆cycloalkyl-C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₂-C₆alkenyloxy, C₂-C₆-haloalkenyloxy, C₃-C₆alkynyloxy,C₃-C₆cycloalkyl-C₁-C₆alkoxy, C₁-C₆alkylthio, C₁-C₆halo-alkylthio,C₂-C₆alkenylthio, C₂-C₆haloalkenylthio, C₃-C₆alkynylthio or byC₃-C₆cycloalkyl-C₁-C₆alkylthio;

(18) compounds of formula (I) according to (1) to (15), wherein E istetrazol-5-yl which is unsubstituted or monosubstituted in the2-position by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆-alkenyl,C₂-C₆haloalkenyl or by C₃-C₆cycloalkyl-C₁-C₆alkyl;

(19) compounds of formula (I) according to (1) to (15), wherein E is1,2,4-oxadiazol-3-yl which is unsubstituted or monosubstituted by CN,halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₃-C₆alkynyl, C₃-C₆cycloalkyl, C₁-C₆alkylcarbonyl,C₁-C₆-haloalkylcarbonyl or by C₁-C₆alkoxycarbonyl;

(20) compounds of formula (I) according to (1) to (15), wherein E isisoxazol-3-yl which is unsubstituted or monosubstituted by halogen,C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy-methyl, C₁-C₆haloalkoxy-methyl,C₁-C₆alkylcarbonyloxy-methyl, C₁-C₆haloal kylcarbonyloxy-methyl,C₁-C₆alkylcarbonyl, C₁-C₆haloalkylcarbonyl or by C₁-C₆alkoxycarbonyl;

(21) compounds of formula (I) according to (1) to (15), wherein E isthiazol-2-yl which is unsubstituted or mono- or disubstituted byhalogen, OH, CN, C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl,C₁-C₆alkylcarbonyl, C₁-C₆haloalkylcarbonyl or by C₁-C₆alkoxycarbonyl,and wherein the substituents are independent of each other;

(22) compounds of formula (I) according to (1) to (15), wherein E is1,3,4-thiadiazol-2-yl which is unsubstituted or monosubstituted byhalogen, CN, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₃-C₆cycloalkyl-C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₃-C₆alkynyloxy,C₃-C₆cycloalkyl-C₁-C₆alkoxy, C₁-C₆-alkylthio, C₁-C₆haloalkylthio,C₂-C₆alkenylthio, C₂-C₆haloalkenylthio, C₃-C₆alkynylthio or byC₃-C₆cycloalkyl-C₁-C₆alkylthio;

(23) compounds of formula (I) according to (1) to (15), wherein E is1,2,4-triazol-3-yl which is unsubstituted or substituted on the nitrogenin the 1-, 2- or 4-position by C₁-C₆alkyl and is unsubstituted orsubstituted in the 5-position by halogen, NO₂, C₁-C₆alkyl,C₁-C₆-haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₃-C₆cycloalkyl-C₁-C₆alkyl, C₁-C₆alkoxy, C₁-C₆-haloalkoxy,C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₃-C₆alkynyloxy,C₃-C₆cycloalkyl-C₁-C₆-alkoxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio,C₂-C₆alkenylthio, C₂-C₆haloalkenylthio, C₃-C₆-alkynylthio,C₃-C₆cycloalkyl-C₁-C₆alkylthio, NH₂, NHC(═O)C₁-C₆alkyl,NHC(═O)C₁-C₆haloalkyl or by NHC(═O)O—C₁-C₆alkyl;

(24) compounds of formula (I) according to (1) to (15), wherein E isthiazol-4-yl, which is mono- or disubstituted by halogen, OH, CN,C₁-C₆alkyl, C₁-C₆haloalkyl, C₃-C₆cycloalkyl, C₁-C₆alkylcarbonyl,C₁-C₆haloalkylcarbonyl or by C₁-C₆alkoxycarbonyl, and wherein thesubstituents are independent of each other;

(25) compounds of formula (I) according to (1) to (24), wherein D is CH;

(26) compounds of formula (I) according to (1) to (24), wherein D is N;

(27) compounds of formula (I) according to (1) to (26), wherein A₀ is—CH₂—;

(28) compounds of formula (I) according to (1) to (26), wherein A₀ is abond.

Special preference is given to the compounds listed in the Tables.

The invention relates also to a process for the preparation of acompound of formula (I), or a salt thereof, wherein

(a) a compound of formula

wherein A₀, A₁, A₂, A₃, D, E, W, Q, T, R₁, R₂, R₃, R₄, m and k are asdefined for formula (I) under (1), Z₁ is —C(═O)R₁₂ and R₁₂ is H orC₁-C₆alkyl, is converted in the presence of an oxidising agent,especially a peracid, into a compound of formulaG-Z_(2a)  (IIIa),

wherein Z_(2a) is O—C(═O)—R₁₃ and R₁₃ is C₁-C₆alkyl, and G denotes thepart of the formula in brackets designated G in formula (II); either

(b) a compound of formula (IIIa) above or of formulaG-Z_(2b)  (IIIb),

wherein G denotes the part of the formula in brackets designated G informula (II), Z_(2b) is a radical of formula —Y—C(═O)R₁₄, Y is asdefined for formula (I) under (1), and R₁₄ is C₁-C₁₂alkyl unsubstitutedor substituted by from one to three identical or different halogensubstituents, or is phenyl unsubstituted or substituted by from one tothree identical or different substituents selected from halogen, CN,nitro, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₁-C₆alkoxycarbonyl and C₂-C₆haloalkenyloxy, is converted by hydrolyticcleavage into a compound of formulaG-Z₃  (IV),

wherein G denotes the part of the formula in brackets designated G informula (II), Z₃ is YH, and Y is as defined for formula (I) under (1);or

(c) a compound of formulaG-Z₄  (V),

wherein Z₄ is Y—CH₂-phenyl, wherein the phenyl radical is unsubstitutedor substituted by from one to three identical or different substituentsselected from halogen, CN, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkylcarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl andC₂-C₆haloalkenyloxy, G denotes the part of the formula in bracketsdesignated G in formula (II), and Y is as defined for formula (I), isconverted by removal of the benzyl group into a compound of formula(IV), as defined above;

(d) the compound of formula (IV) so obtained is reacted in the presenceof a base with a compound of formula

wherein Hal is halogen, preferably bromine or chlorine, and alkyl isC₁-C₆alkyl, or the two alkyl radicals together form a C₃-C₈alkylenebridge, to form a compound of formulaG-Z₅  (VI),

wherein G denotes the part of the formula in brackets designated G informula (II), and Z₅ is

wherein alkyl and Y are as defined above;

(e) the compound of formula (VI) so obtained is converted bydeprotection of the acetal function in the presence of an acid into acompound of formulaG-Z₆  (VII),

wherein Z₆ is a group —Y—CH₂—C(═O)H, G is as defined above for thecompound of formula (II), and Y is as defined for formula (I) under (1),either

(f₁) for the preparation of a compound of formula (I) wherein X₁ and X₂are chlorine or bromine, a compound of formula (VII) is reacted in thepresence of a phosphine with a compound of formula C(X)₄ wherein X ischlorine or bromine; or

(f₂) for the preparation of a compound of formula (I) wherein X₁ and X₂are chlorine, a compound of formula (VII) is reacted first withCCl₃—COOH or with chloroform in the presence of a strong base, then withacetic anhydride and subsequently with powdered zinc in acetic acid; or

(f₃) for the preparation of a compound of formula (I) wherein X₁ isfluorine and X₂ is chlorine or bromine, a compound of formula (VII) isreacted in the presence of a phosphine with a compound of the formulaCF₂X₂, of the formula CFX₃, of the formula CF₂XCOONa or of the formulaCFX₂COONa; or

(g₁) for the preparation of a compound of formula (I) wherein X₁ and X₂are chlorine or bromine, a compound of formula (IV) is reacted in thepresence of a base with a compound of formula

wherein L₃ is a leaving group, preferably chlorine or bromine, and Halis chlorine or bromine; or

(g₂) for the preparation of a compound of formula (I) wherein X₁ and X₂are chlorine or bromine, a compound of formula (IV) is reacted in thepresence of a base with a compound of formula

wherein Hal is halogen and X is chlorine or bromine.

The invention relates also to

(h) a process for the preparation of a compound of formula (I) asdefined under (1) and wherein Q is O, NR₆ or S and R₆ is as defined forformula (I) under (1), wherein a compound of formula

wherein A₀, A₁, A₂, A₃, D, E, W, T, R₄, R₅, R₆ and k are as defined forformula (I) under (1) and L₁ is a leaving group, is reacted in thepresence of a base with a compound of formula

wherein R₁, R₂, R₃ and m are as defined for formula (I) under (1), Q isO, NR₆ or S and Z is one of the radicals Z₁ to Z₆ as defined for theabove formulae (II) to (VII), and R₆ is as defined for formula (I) under(1), and the resulting compound of formula

wherein A₀, A₁, A₂, A₃, D, E, W, Q, T, R₁, R₂, R₃, R₄, m and k are asdefined for formula (I) under (1) and Z is one of the radicals Z₁ to Z₆as defined for formulae (II) to (VII) indicated above, is, as necessary,that is to say according to the meaning of the radical Z, reactedfurther analogously to one or more of process steps (a) to (g).

In the compounds of formulae X/a to X/f, Z in compound X/a has the samemeanings as Z₁ in the compound of formula (II), and Z in compound X/bhas the same meanings as Z₂ as defined for formula (III), and so on.

The invention relates also to

(i₁) a process for the preparation of a compound of formula (I) asdefined above wherein W is O, NR₆, S, —O—C(═O)— or —NR₇—C(═O)— and R₆and R₇ are as defined for formula (I) under (1), wherein a compound offormula

wherein A₀, A₁, A₂, A₃, D, T, R₄ and k are as defined for formula (I)under (1), W₁ is O, NR₆, S or —NR₇— and R₆ is as defined for formula (I)under (1), is reacted with a compound of formula

wherein A₃, R₁, R₂, R₃, Q and m are as defined for formula (I) under(1), L₂ is a leaving group or a group Hal-C(═O)— wherein Hal is ahalogen atom, preferably chlorine or bromine, and Z is one of theradicals Z₁ to Z₆ as defined in formulae (II) to (VII) indicated above;or

(i₂) for the preparation of a compound of formula (I) as defined abovewherein W is O, NR₆, S, —C(═O)—O— or —C(═O)—NR₇— and R₆ and R₇ are asdefined for formula (I) under (1), wherein a compound of formula

wherein A₀, A₁, A₂, D, E, T, R₄ and k are as defined for formula (I)under (1) and L₁ is a leaving group or a group —C(═O)—Hal wherein Hal isa halogen atom, preferably chlorine or bromine, is reacted with acompound of formula

wherein W₂ is O, NR₆, S or NR₇ and R₁, R₂, R₃ and m are as defined forformula (I) under (1),

and a resulting compound of formula (Xa) to (Xf) as defined above is, asnecessary, that is to say according to the meaning of the radical Z,reacted further analogously to one or more of process steps (a) to (g).

In the compounds of formulae XII/a to XII/f and XIV/a to XIV/f, theradicals Z are as defined above for the compounds X/a to X/f; that is tosay, for example, Z in the compound of formula XII/a has the samemeanings as Z₁ in the compound of formula (II), and Z in compound XII/bhas the same meanings as Z₂ as defined for formula (III), and so on.

The invention relates also to

(k) a process for the preparation of a compound of formula (I) asdefined above under (1), wherein a compound of formula (VIII) as definedabove is reacted in the presence of a base with a compound of formula

wherein R₁, R₂, R₃, Q, X₁, X₂, Y and m are as defined for formula (I)under (1).

The invention relates also to

(l) a process for the preparation of a compound of formula (I) asdefined above under (1), wherein a compound of formula (XI) as definedabove is reacted in a manner analogous to that in process variant (i)with a compound of formula

wherein A₃, R₁, R₂, R₃, Q, Y, X₁, X₂ and m are as defined for formula(I) under (1) and L₂ is as defined for formula (XII).

The compounds of formulae (IIIa) and (IIIb) wherein R₁ and R₂ arehalogen can be obtained by reacting a compound of formula

wherein R₃, Q, Y and m are as defined for formula (I) under (1), with acompound of the formula Hal-C(═O)—R₁₃ wherein R₁₃ is as defined above,halogenating the resulting compound of formula

wherein R₃, Q, Y and m are as defined for formula (I) under (1), andfurther reacting the resulting compound of formula

wherein R₃, Q, Y and m are as defined for formula (I) under (1) and R₁and R₂ are halogen, analogously to Process (k).

The invention relates also to

(m) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E isunsubstituted or substituted 1,2,3,4-tetrazol-5-yl, wherein any compoundof formula (II), (III), (IV), (V), (VI), (VII), (VIII), (X), (XI) or(XIII) wherein CN is present instead of the heterocyclic radical E isreacted with sodium azide and then substituted further, if desired.

The invention relates also to

(n) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E isunsubstituted or substituted 1,2,3,4-tetrazol-1-yl, wherein any compoundof formula (II), (III), (IV), (V), (VI), (VII), (VIII), (X), (XI) or(XIII), wherein NCS is present instead of the heterocyclic radical E, isreacted with sodium azide and then substituted further, if desired.

The invention relates also to

(o) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E isunsubstituted or substituted 1,2,4-oxadiazol-3-yl, wherein any compoundof formula (II), (III), (IV), (V), (VI), (VII), (VIII), (X), (XI) or(XIII) wherein CN is present instead of the heterocyclic radical E isreacted with hydroxylamine and then with an acid chloride, acidanhydride or orthoformic acid ester, and is then substituted further, ifdesired.

The invention relates also to

(p) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E isisoxazol-3-yl, wherein any compound of formula (II), (III), (IV), (V),(VI), (VII), (VIII), (X), (XI) or (XIII), wherein CHO is present insteadof the heterocyclic radical E, is reacted with hydroxylamine, then witha halogenating agent and subsequently, in the presence of a base, withan alkyne.

The invention relates also to

(q) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E is5-chloro-isoxazol-3-yl, wherein any compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII), wherein CHO ispresent instead of the heterocyclic radical E, is reacted withhydroxylamine, then with a halogenating agent and subsequently, in thepresence of a base, with 1,1-dichloroethane.

The invention relates also to

(r) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E isthiazol-2-yl, said thiazole optionally being substituted in the4-position with alkyl, haloalkyl, hydroxyalkyl, cycloalkyl,cycloalkyl-alkyl, alkenyl, halo-alkenyl, alkynyl or haloalkynyl, whereinany compound of formula (II), (III), (IV), (V), (VI), (VII), (VIII),(X), (XI) or (XIII), wherein C(═S)NH₂ is present instead of theheterocyclic radical E, is reacted with a suitable α-haloketone or anα-halocarboxylic acid ester; or

(s) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E isthiazol-4-yl, said thiazole optionally being substituted in the 2- andin the 4-position indepentdently of each other with alkyl, haloalkyl,hydroxyalkyl, cycloalkyl, cycloalkyl-alkyl, alkenyl, haloalkenyl,alkynyl or haloalkynyl, wherein any compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII), wherein—C(═O)C₁-C₄alkyl is present instead of the heterocyclic radical E, isreacted with an halogenating agent followed by a reaction with asuitable thioamide;

The invention relates also to

(t) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E is1,3,4-thiadiazol-2-yl, wherein any compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII), wherein B(OH)₂ ispresent instead of the heterocyclic radical E, is reacted in thepresence of a palladium catalyst with a 2-halo-1,3,4-thiadiazole.

The invention relates also to

(t1) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E is1,3,4-thiadiazol-2-yl, wherein any compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII), wherein halogen orOS(O₂)CF₃ is present instead of the heterocyclic radical E, is reactedin the presence of a palladium catalyst with 1,3,4-thiadiazole-2-boronicacid or a 1,3,4-thiadiazole-2-boronic acid ester.

The invention relates also to

(u) a process for the preparation of a compound of formula (II), (III),(IV), (V), (VI), (VII), (VIII), (X), (XI) or (XIII) wherein E is1,2,4-triazol-3-yl, wherein any compound of formula (II), (III), (IV),(V), (VI), (VII), (VIII), (X), (XI) or (XIII), wherein —C(═NH)NH₂ ispresent instead of the heterocyclic radical E, is reacted in thepresence of a base with a carboxylic acid hydrazide.

The reactions described hereinabove and hereinbelow are carried out in amanner known per se, for example in the absence or, where appropriate,in the presence of a suitable solvent or diluent or of a mixturethereof, the reactions being carried out, as required, with cooling, atroom temperature or with heating, for example in a temperature range ofapproximately from −80° C. to the boiling temperature of the reactionmixture, preferably from approximately −20° C. to approximately +150°C., and, if necessary, in a closed vessel, under pressure, under aninert gas atmosphere and/or under anhydrous conditions. Especiallyadvantageous reaction conditions can be found in the Examples.

A leaving group, for example the leaving groups L₁ and L₂ defined above,or a counterion is to be understood hereinabove and hereinbelow as beingany removable group that customarily comes into consideration forchemical reactions, such as are known to the person skilled in the art;especially OH, halogens, such as fluorine, chlorine, bromine, iodine,—O—Si(C₁-C₈alkyl)₃, —O-aryl, —S—(C₁-C₈alkyl), —S-aryl, —O—S(═O)₂U,—S(═O)U or —S(═O)₂U, wherein U is unsubstituted or substitutedC₁-C₈alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl, unsubstituted or substitutedaryl or unsubstituted or substituted benzyl. Especially preferred asleaving group are chlorine and bromine, mesylate, triflate, tosylate,especially chlorine; and chloride and bromide, especially chloride.

Process (a): The reaction is carried out in acetic acid or a halogenatedhydrocarbon, such as dichloromethane, at temperatures of from −20° C. to100° C., preferably at from 20° C. to 50° C. As oxidising agents thereare used, for example, hydrogen peroxide, a peracid, such as peraceticacid, trifluoroperacetic acid, 3-chloroperbenzoic acid or a mixturethereof, such as sodium perborate in acetic acid.

Process (b): The reaction is preferably carried out in an alcohol, suchas methanol, ethanol or an alcohol/water mixture, in the presence of aninorganic base, such as NaOH or KOH, and at temperatures of from 0° C.to 150° C., preferably from 20° C. to 80° C. Alternatively aminolysiswith a primary amine, such as n-butylamine, can be carried out in ahydrocarbon, such as toluene or benzene, at temperatures of from 0° C.to 150° C., preferably at from 20° C. to 80° C.

Process (c): Depending upon the nature of the benzyl substituent to beremoved, the reaction can be carried out, for example, under a hydrogenatmosphere, at a pressure of from 1 to 150 bar, especially at from 1 to20 bar, and with the addition of a catalyst, such as palladium/carbon,in an alcohol or ether. The preferred reaction temperature is from 0° C.to 120° C., especially from 20° C. to 80° C.

Processes (d) and (g): The reactions are preferably carried out in thepresence of a base, such as potassium or sodium carbonate, in acetone ordimethylformamide, at temperatures of from 0° C. to 150° C., preferablyfrom 20° C. to 80° C. If necessary, catalytic amounts of potassiumiodide or sodium iodide, or phase transfer catalysts, such as crownethers or quaternary ammonium salts, are added.

Process (e): The reaction is preferably carried out in acetone,dichloromethane, acetic acid, or especially in water, optionally withthe addition of a mineral acid, at temperatures of from 0° C. to 120°C., preferably at from 20° C. to 50° C. For complete cleavage of theacetal it is preferable to add a strong mineral acid, for examplehydrochloric acid, sulfuric acid or 4-toluenesulfonic acid.

Process (f): For the preparation of the difluoro-, dichloro-, dibromo-,chlorofluoro- and bromofluoro-vinyl compounds, reaction with CCl₄, CBr₄,CF₂X₂, CFX₃, CF₂XC(═O)ONa or CFX₂C(═O)ONa wherein X is bromine orchlorine is carried out in the presence of a trialkyl- ortriaryl-phosphine, optionally with the addition of powdered zinc. Thereaction is carried out in an inert solvent such as, for example,benzene or toluene, or an ether, such as diethyl ether, diisopropylether, dioxane or tetrahydrofuran, at temperatures of from 0° C. to 150°C., preferably at from 20° C. to 80° C.

For the preparation of the dichlorovinyl compounds it is also possiblefor the process to be carried out in dimethylformamide, benzene,toluene, or in an ether, at temperatures of from 0° C. to 120° C.,preferably from 20° C. to 80° C., and in the presence of trichloroaceticacid/sodium trichloroacetate, then by addition of acetic anhydride,optionally with the addition of base, for example triethylamine, andfinally by addition of zinc and acetic acid.

Processes (h) and (k): The reactions are preferably carried out in anether, dimethyl-formamide, dimethylacetamide or N-methylpyrrolidone, attemperatures of from 0° C. to 150° C., preferably at from 20° C. to 80°C., with the addition of a base, such as potassium or sodium carbonate.Alternatively a coupling reagent, for example azodicarboxylic aciddiethyl or diisopropyl ester and triphenylphosphine, can be used.

Processes (i) and (l):

Where L₂ is a group Hal-C(═O)—, the process can be carried out in aninert solvent, such as in an ether or in toluene, at from 0° C. to 80°C., and in the presence of a suitable base, for example a trialkylamine.

In the other cases the reaction is carried out in an ether, in an amide,such as dimethylformamide or N-methylpyrrolidone, and at from 0° C. to150° C. Sodium hydride, for example, can be used as base.

Process (m): There are suitable as solvents, for example, toluene,benzene, ethanol, propanol, isopropanol, methoxyethanol, ethoxyethanolor dimethylformamide. The reaction is carried out at from 20 to 200° C.,preferably at from 80 to 150° C., where appropriate with the addition oflithium chloride, ammonium chloride or triethylammonium chloride.

The further reaction is carried out, for example, in dimethylformamide,dimethyl sulfoxide, tetrahydrofuran, acetonitrile or toluene, in thepresence of a base, for example potassium or sodium carbonate.

Process (n): The reaction is carried out, for example, in toluene,benzene, dioxane, tetrahydrofuran, dimethylformamide orN-methylpyrrolidone, at from 0 to 130° C., preferably at from 20 to 80°C.

Process (o): The reaction is carried out with hydroxylaminehydrochloride in the presence of a base, such as triethylamine, forexample in ethanol, isopropanol, dimethylformamide orN-methylpyrrolidone, at from 0 to 120° C., preferably at from 20 to 80°C.

The further reaction is carried out, for example, in toluene, benzene,THF, dioxane or dichloromethane, at from 0 to 120° C. in the presence ofa base, such as triethylamine or pyridine.

Process (p): The reaction with hydroxylamine hydrochloride is carriedout in the presence of a base, such as triethylamine. The halogenationof the resulting oxime is carried out, for example, using sodiumhypochlorite or tert-butyl hypochlorite in carbon tetrachloride,chloroform or dichloromethane.

The further reaction with an alkyne is carried out in the presence of abase, such as triethylamine or pyridine, at from −20 to 120° C.,preferably at from 0 to 80° C.

Process (q): The process is carried out analogously to procedure (p).Instead of an alkyne, 1,1-dichloroethane is used.

Processes (r) and (s): The reaction is carried out, for example, inethanol, propanol or dimethylformamide, at from 0 to 120° C., preferablyat from 20 to 80° C.

Process (t): The Reaction is for example carried out in toluene,benzene, an ether, such as dimethoxyethane, in the presence of a base,for example aqueous sodium carbonate solution, and a palladium catalyst,such as palladium tetrakis(triphenylphosphine), at temperatures of from0 to 150° C., preferably at from 20 to 100° C.

Process (u): The reaction of the amidine is carried out, for example, inbenzene, toluene, diethyl ether, diisopropyl ether, tert-butyl methylether, in the presence of a base, for example potassium or sodiumhydroxide, at from 0 to 150° C., preferably at from 20 to 100° C.

It will be understood that in the above-described Processes (m) to (u),in which a compound of formula (II), (III), (IV), (V), (VI), (VII),(VIII), (X), (XI) or (XIII) carrying a substituent, such as CN, —NCS,B(OH)₂, —OS(O₂)CF₃, —C(═O)O-alkyl, —C(═NH)NH₂, I, Br or CHO instead ofthe heterocyclic radical E is processed further, further functionalgroups likewise carried by those intermediate compounds must undercertain circumstances be protected by protecting groups. Such protectinggroups are introduced according to the nature of the substituent inquestion. They include any removable group that customarily comes intoconsideration for chemical reactions, such as are known to the personskilled in the art. For example, aldehyde and keto groups are protectedin the form of acetals or ketals, acids in the form of their esters,hydroxy groups in the form of ethers or esters, and phenolic hydroxygroups in the form of benzyl ethers or methyl ethers.

Compounds of formula (I) obtainable in accordance with the process or byother means can be converted into other compounds of formula (I) in amanner known per se by replacement of one or more substituents in thestarting compound of formula (I) in customary manner by another (other)substituent(s) according to the invention.

In the case of such replacement, depending upon the choice of reactionconditions and starting materials suitable therefor, it is possible foronly one substituent to be replaced by another substituent according tothe invention in a reaction step or for a plurality of substituents tobe replaced by other substituents according to the invention in the samereaction step.

Salts of compounds of formula (I) can be prepared in a manner known perse. For example, salts of compounds of formula (I) with bases areobtained by treatment of the free compounds with a suitable base or witha suitable ion exchange reagent.

Salts of compounds of formula (I) can be converted into the freecompounds of formula (I) in customary manner, for example by treatmentwith a suitable acid or with a suitable ion exchange reagent.

Salts of compounds of formula (I) can be converted in a manner known perse into other salts of a compound of formula (I).

The compounds of formula (I), in free form or in salt form, may be inthe form of one of the possible isomers or in the form of a mixturethereof, for example, depending upon the number of asymmetric carbonatoms occurring in the molecule and their absolute and relativeconfiguration, and/or depending upon the configuration of non-aromaticdouble bonds occurring in the molecule, in the form of pure isomers,such as antipodes and/or diastereoisomers, or in the form of mixtures ofisomers, such as mixtures of enantiomers, for example racemates,mixtures of diastereoisomers or mixtures of racemates. The inventionrelates both to the pure isomers and to all possible mixtures of isomersand is to be interpreted as such hereinbefore and hereinafter, even ifstereochemical details are not mentioned specifically in every case.

Mixtures of diastereoisomers, mixtures of racemates and mixtures ofdouble bond isomers of compounds of formula (I), in free form or in saltform, which may be obtained in accordance with the process—dependingupon the starting materials and procedures chosen—or by some othermethod, can be separated into the pure diastereoisomers or racemates inknown manner on the basis of the physico-chemical differences betweenthe constituents, for example by means of fractional crystallisation,distillation and/or chromatography.

Mixtures of enantiomers, such as racemates, that are obtainable in acorresponding manner can be resolved into the enantiomers by knownmethods, for example by recrystallisation from an optically activesolvent, by chromatography on chiral adsorbents, for example highpressure liquid chromatography (HPLC) on acetylcellulose, with the aidof suitable microorganisms, by cleavage with specific, immobilisedenzymes, via the formation of inclusion compounds, for example usingchiral crown ethers, only one enantiomer being complexed, or byconversion into diastereoisomeric salts and separation of the mixture ofdiastereoisomers so obtained, for example on the basis of theirdifferent solubilities by fractional crystallisation, into thediastereoisomers, from which the desired enantiomer can be freed by theaction of suitable agents.

Apart from by separation of corresponding mixtures of isomers, purediastereoisomers or enantiomers can be obtained according to theinvention also by generally known methods of diastereoselective orenantioselective synthesis, for example by carrying out the processaccording to the invention using starting materials havingcorrespondingly suitable stereo-chemistry.

In each case it is advantageous to isolate or synthesise thebiologically more active isomer, e.g. enantiomer or diastereoisomer, orisomeric mixture, e.g. enantiomeric mixture or diastereoisomericmixture, where the individual components have different biologicalactivity.

The compounds of formula (I), in free form or in salt form, can also beobtained in the form of their hydrates and/or may include othersolvents, for example solvents which may have been used for thecrystallisation of compounds in solid form.

The invention relates to all those embodiments of the process accordingto which a compound obtainable as starting material or intermediate atany stage of the process is used as starting material and some or all ofthe remaining steps are carried out or a starting material is used inthe form of a derivative or salt and/or its racemates or antipodes or,especially, is formed under the reaction conditions.

In the process of the present invention it is preferable to use thosestarting materials and intermediates, in each case in free form or insalt form, which result in the compounds of formula (I) and their saltsdescribed at the beginning as being especially valuable.

The invention relates especially to the preparation processes describedin Examples P1 to P11.

The invention relates also to the intermediates of formulae (II) to(XIX), where novel, and to the corresponding compounds wherein CN, NCS,C(H)O, B(OH)₂, —C(H)═NOH, —C(Cl)═NOH, —C(═NH)NH₂ or —C(═S)NH₂ is presentinstead of the heterocyclic radical E, and, where applicable, to theirpossible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in eachcase in free form or in salt form. The preferences applying to suchcompounds are the same as those for the compounds of formula (I).

In the area of pest control, the compounds of formula (I) according tothe invention are active ingredients exhibiting valuable preventiveand/or curative activity with a very advantageous biocidal spectrum anda very broad spectrum, even at low rates of concentration, while beingwell tolerated by warm-blooded animals, fish and plants. They are,surprisingly, equally suitable for controlling both plant pests andecto- and endo-parasites in humans and more especially in productivelivestock, domestic animals and pets. They are effective against all orindividual development stages of normally sensitive animal pests, butalso of resistant animal pests, such as insects and representatives ofthe order Acarina, nematodes, cestodes and trematodes, while at the sametime protecting useful organisms. The insecticidal or acaricidalactivity of the active ingredients according to the invention maymanifest itself directly, i.e. in the mortality of the pests, whichoccurs immediately or only after some time, for example during moulting,or indirectly, for example in reduced oviposition and/or hatching rate,good activity corresponding to a mortality of at least 50 to 60%.

Successful control within the scope of the subject of the invention ispossible, in particular, of pests from the orders Lepidoptera,Coleoptera, Orthoptera, Isoptera, Psocoptera, Anoplura, Mallophaga,Thysanoptera, Heteroptera, Homoptera, Hymenoptera, Diptera,Siphonaptera, Thysanura and Acarina, mainly Acarina, Diptera,Thysanoptera, Lepidoptera and Coleoptera. Very especially good controlis possible of the following pest:

Abagrotis spp., Abraxas spp., Acantholeucania spp., Acanthoplusia spp.,Acarus spp., Acarus siro, Aceria spp., Aceria sheldoni, Acleris spp.,Acoloithus spp., Acompsia spp., Acossus spp., Acria spp., Acrobasisspp., Acrocercops spp., Acrolepia spp., Acrolepiopsis spp., Acronictaspp., Acropolitis spp., Actebia spp., Aculus spp., Aculusschlechtendali, Adoxophyes spp., Adoxophyes reticulana, Aedes spp.,Aegeria spp., Aethes spp., Agapeta spp., Agonopterix spp., Agriopisspp., Agriotes spp., Agriphila spp., Agrochola spp., Agroperina spp.,Alabama ssp., Alabama argillaceae, Agrotis spp., Albuna spp., Alcathoespp., Alcis spp., Aleimma spp., Aletia spp., Aleurothrixus spp.,Aleurothrixus floccosus, Aleyrodes spp., Aleyrodes brassicae, Allophyesspp., Alsophila spp., Amata spp., Amathes spp., Amblyomma spp.,Amblyptilia spp., Ammoconia spp., Amorbia spp., Amphion spp., Amphipoeaspp., Amphipyra spp., Amyelois spp., Anacamptodes spp., Anagrapha spp.,Anarsia spp., Anatrychyntis spp., Anavitrinella spp., Ancylis spp.,Andropolia spp., Anhimella spp., Antheraea spp., Antherigona spp.,Antherigona soccata, Anthonomus ssp., Anthonomus grandis, Anticarsiaspp., Anticarsia gemmatalis, Aonidiella spp., Apamea spp., Aphania spp.,Aphelia spp., Aphididae, Aphis spp., Apotomis spp., Aproaerema spp.,Archippus spp., Archips spp., Acromyrmex, Arctia spp., Argas spp.,Argolamprotes spp., Argyresthia spp., Argyrogramma spp., Argyroplocespp., Argyrotaenia spp., Arotrophora spp., Ascotis spp., Aspidiotusspp., Aspilapteryx spp., Asthenoptycha spp., Aterpia spp., Athetis spp.,Atomaria spp., Atomaria linearis, Atta spp., Atypha spp., Autographaspp., Axylia spp., Bactra spp., Barbara spp., Batrachedra spp.,Battaristis spp., Bembecia spp., Bemisia spp., Bemisia tabaci, Bibiospp., Bibio hortulanis, Bisigna spp., Blastesthia spp., Blatta spp.,Blatella spp., Blepharosis spp., Bleptina spp., Boarmia spp., Bombyxspp., Bomolocha spp., Boophilus spp., Brachmia spp., Bradina spp.,Brevipalpus spp., Brithys spp., Bryobia spp., Bryobia praetiosa,Bryotropha spp., Bupalus spp., Busseola spp., Busseola fusca, Caberaspp., Cacoecimorpha spp., Cadra spp., Cadra cautella, Caenurgina spp.,Calipitrimerus spp., Callierges spp., Callophpora spp., Callophporaerythrocephala, Calophasia spp., Caloptilia spp., Calybites spp.,Capnoptycha spp., Capua spp., Caradrina spp., Caripeta spp., Carmentaspp., Carposina spp., Carposina nipponensis, Catamacta spp., Catelaphrisspp., Catoptria spp., Caustoloma spp., Celaena spp., Celypha spp.,Cenopis spp., Cephus spp., Ceramica spp., Cerapteryx spp., Ceratitisspp, Ceratophyllus spp., Ceroplaster spp., Chaetocnema spp., Chaetocnematibialis, Chamaesphecia spp., Charanvca spp., Cheimophila spp.,Chersotis spp., Chiasmia spp., Chilo spp., Chionodes spp., Chorioptesspp., Choristoneura spp., Chrysaspidia spp., Chrysodeixis spp.,Chrysomya spp., Chrysomphalus spp., Chrysomphalus dictyospermi,Chrysomphalus aonidium, Chrysoteuchia spp., Cilix spp., Cimex spp.,Clysia spp., Clysia ambiguella, Clepsis spp., Cnaemidophorus spp.,Cnaphalocrocis spp., Cnephasia spp., Coccus spp., Coccus hesperidum,Cochylis spp., Coleophora spp., Colotois spp., Commophila spp., Conistraspp., Conopomorpha spp., Corcyra spp., Cornutiplusia spp., Cosmia spp.,Cosmopolites spp., Cosmopterix spp., Cossus spp., Costaeonvexa spp.,Crambus spp., Creatonotos spp., Crocidolomia spp., Crocidolomiabinotalis, Croesia spp., Crymodes spp., Cryptaspasma spp., Cryptoblabesspp., Cryptocala spp., Cryptophlebia spp., Cryptophlebia leucotreta,Cryptoptila spp., Ctenopseustis spp., Cucullia spp., Curculio spp.,Culex spp., Cuterebra spp., Cydia spp., Cydia pomonella, Cymbalophoraspp., Dactylethra spp., Dacus spp., Dadica spp., Damalinea spp.,Dasychira spp., Decadarchis spp., Decodes spp., Deilephila spp.,Deltodes spp., Dendrolimus spp., Depressaria spp., Dermestes spp.,Dermanyssus spp., Dermanyssus gallinae, Diabrotica spp., Diachrysiaspp., Diaphania spp., Diarsia spp., Diasemia spp., Diatraea spp.,Diceratura spp., Dichomeris spp., Dichrocrocis spp., Dichrorampha spp.,Dicycla spp., Dioryctria spp., Diparopsis spp., Diparopsis castanea,Dipleurina spp., Diprion spp., Diprionidae, Discestra spp., Distantiellaspp., Distantiella theobroma, Ditula spp., Diurnea spp., Doratopteryxspp., Drepana spp., Drosphila spp., Drosphila melanogaster, Dysauxesspp., Dysdercus spp., Dysstroma spp., Eana spp., Earias spp., Eccliticaspp., Ecdytolopha spp., Ecpyrrhorrhoe spp., Ectomyelois spp., Eetropisspp., Egira spp., Elasmopalpus spp., Emmelia spp., mpoasca spp.,Empyreuma spp., Enargia spp., Enarmonia spp., Endopiza spp., Endotheniaspp., Endotricha spp., Eoreuma spp., Eotetranychus spp., Eotetranychuscarpini, Epagoge spp., Epelis spp., Ephestia spp., Ephestiodes spp.,Epiblema spp., Epiehoristodes spp., Epinotia spp., Epiphyas spp.,Epiplema spp., Epipsestis spp., Epirrhoe spp., Episimus spp., Epitymbiaspp., Epilachna spp., Erannis spp., Erastria spp., Eremnus spp.,Ereunetis spp., Eriophyes spp., Eriosoma spp., Eriosoma lanigerum,Erythroneura spp., Estigmene spp., Ethmia spp., Etiella spp., Euagrotisspp., Eucosma spp., Euehlaena spp., Euelidia spp., Eueosma spp.,Euchistus spp., Eucosmomorpha spp., Eudonia spp., Eufidonia spp.,Euhyponomeutoides spp., Eulepitodes spp., Eulia spp., Eulithis spp.,Eupithecia spp., Euplexia spp., Eupoecilia spp., Eupoecilia ambiguella,Euproctis spp., Eupsilia spp., Eurhodope spp., Eurois spp., Eurygasterspp., Eurythmia spp., Eustrotia spp., Euxoa spp., Euzophera spp.,Evergestis spp., Evippe spp., Exartema spp., Fannia spp., Faronta spp.,Feltia spp., Filatima spp., Fishia spp., Frankliniella spp., Fumibotysspp., Gaesa spp., Gasgardia spp., Gastrophilus spp., Gelechia spp.,Gilpinia spp., Gilpinia polytoma, Glossina spp., Glyphipterix spp.,Glyphodes spp., Gnorimoschemini spp., Gonodonta spp., Gortyna spp.,Gracillaria spp., Graphania spp., Grapholita spp., Grapholitha spp.,Gravitarmata spp., Gretchena spp., Griselda spp., Gryllotalpa spp.,Gynaephora spp., Gypsonoma spp., Hada spp., Haematopinus spp.,Halisidota spp., Harpipteryx spp., Harrisina spp., Hedya spp.,Helicoverpa spp., Heliophobus spp., Heliothis spp., Hellula spp.,Helotropa spp., Hemaris spp., Hercinothrips spp., Herculia spp.,Hermonassa spp., Heterogenea spp., Holomelina spp., Homadaula spp.,Homoeosoma spp., Homoglaea spp., Homohadena spp., Homona spp.,Homonopsis spp., Hoplocampa spp., Hoplodrina spp., Hoshinoa spp.,Hxalomma spp., Hydraecia spp., Hydriomena spp., Hyles spp., Hyloicusspp., Hypagyrtis spp., Hypatima spp., Hyphantria spp., Hyphantria cunea,Hypocala spp., Hypocoena spp., Hypodema spp., Hyppobosca spp., Hypsipylaspp., Hyssia spp., Hysterosia spp., Idaea spp., Idia spp., Ipimorphaspp., Isia spp., Isochorista spp., Isophrictis spp., Isopolia spp.,Isotrias spp., Ixodes spp., Itame spp., Jodia spp., Jodis spp., Kawabeaspp., Keiteria spp., Keiferia lycopersicella, Labdia spp., Lacinipoliaspp., Lambdina spp., Lamprothritpa spp., Laodelphax spp., Lasius spp.,Laspeyresia spp., Leptinotarsa spp., Leptinotarsa decemlineata,Leptocorisa spp., Leptostales spp., Lecanium spp., Lecanium comi,Lepidosaphes spp., Lepisma spp., Lepisma saccharina, Lesmone spp.,Leucania spp., Leucinodes spp., Leucophaea spp., Leucophaea maderae,Leucoptera spp., Leucoptera scitella, Linognathus spp., Liposcelis spp.,Lissorhoptrus spp., Lithacodia spp., Lithocolletis spp., Lithomoia spp.,Lithophane spp., Lixodessa spp., Lobesia spp., Lobesia botrana,Lobophora spp., Locusta spp., Lomanaltes spp., Lomographa spp.,Loxagrotis spp., Loxostege spp., Lucilia spp., Lymantria spp., Lymnaeciaspp., Lyonetia spp., Lyriomyza spp., Macdonnoughia spp., Macrauzataspp., Macronoctua spp., Macrosiphus spp., Malacosoma spp., Maliarphaspp., Mamestra spp., Mamestra brassicae, Manduca spp., Manduca sexta,Marasmia spp., Margaritia spp., Matratinea spp., Matsumuraeses spp.,Melanagromyza spp., Melipotes spp., Melissopus spp., Melittia spp.,Melolontha spp., Meristis spp., Meritastis spp., Merophyas spp.,Mesapamea spp., Mesogona spp., Mesoleuca spp., Metanema spp.,Metendothenia spp., Metzneria spp., Micardia spp., Microcorses spp.,Microleon spp., Mnesictena spp., Mocis spp., Monima spp., Monochroaspp., Monomorium spp., Monomorium pharaonis, Monopsis spp., Morrisoniaspp., Musca spp., Mutuuraia spp., Myelois spp., Mythimna spp., Myzusspp., Naranga spp., Nedra spp., Nemapogon spp., Neodiprion spp.,Neosphaleroptera spp., Nephelodes spp., Nephotettix spp., Nezara spp.,Nilaparvata spp., Niphonympha spp., Nippoptilia spp., Noctua spp., Nolaspp., Notocelia spp., Notodonta spp., Nudaurelia spp., Ochropleura spp.,Ocnerostoma spp., Oestrus spp., Olethreutes spp., Oligia spp., Olindiaspp., Olygonychus spp., Olygonychus gallinae, Oncocnemis spp.,Operophtera spp., Ophisma spp., Opogona spp., Oraesia spp., Orniodorosspp., Orgyia spp., Oria spp., Orseolia spp., Orthodes spp., Orthogoniaspp., Orthosia spp., Oryzaephilus spp., Oscinella spp., Oscinella frit,Osminia spp., Ostrinia spp., Ostrinia nubilalis, Otiorhynchus spp.,Ourapteryx spp., Pachetra spp., Pachysphinx spp., Pagyda spp.,Paleacrita spp., Paliga spp., Palthis spp., Pammene spp., Pandemis spp.,Panemeria spp., Panolis spp., Panolis flammea, Panonychus spp.,Parargyresthia spp., Paradiarsia spp., Paralobesia spp., Paranthrenespp., Parapandemis spp., Parapediasia spp., Parastichtis spp.,Parasyndemis spp., Paratoria spp., Pareromeme spp., Pectinophora spp.,Pectinophora gossypiella, Pediculus spp., Pegomyia spp., Pegomyiahyoscyami, Pelochrista spp., Pennisetia spp., Penstemonia spp.,Pemphigus spp., Peribatodes spp., Peridroma spp., Perileucoptera spp.,Periplaneta spp., Perizoma spp., Petrova spp., Pexicopia spp., Phaloniaspp., Phalonidia spp., Phaneta spp., Phiyctaenia spp., Phlyctinus spp.,Phorbia spp., Phragmatobia spp., Phricanthes spp., Phthorimaea spp.,Phthorimaea operculella, Phyllocnistis spp., Phyllocoptruta spp.,Phyllocoptruta oleivora, Phyllonorycter spp., Phyllophila spp.,Phylloxera spp., Pieris spp., Pieris rapae, Piesma spp., Planococusspp., Planotortrix spp., Platyedra spp., Platynota spp., Platyptiliaspp., Platysenta spp., Plodia spp., Plusia spp., Plutella spp., Plutellaxyiostella, Podosesia spp., Polia spp., Popillia spp., Polymixis spp.,Polyphagotarsonemus spp., Polyphagotarsonemus latus, Prays spp.,Prionoxystus spp., Probole spp., Proceras spp., Prochoerodes spp.,Proeulia spp., Proschistis spp., Proselena spp., Proserpinus spp.,Protagrotis spp., Proteoteras spp., Protobathra spp., Protoschinia spp.,Pselnophorus spp., Pseudaletia spp., Pseudanthonomus spp.,Pseudaternelia spp., Pseudaulacaspis spp., Pseudexentera spp.,Pseudococus spp., Pseudohermenias spp., Pseudoplusia spp., Psoroptesspp., Psylla spp., Psylliodes spp., Pterophorus spp., Ptycholoma spp.,Pulvinaria spp., Pulvinaria aethiopica, Pyralis spp., Pyrausta spp.,Pyrgotis spp., Pyrreferra spp., Pyrrharctia spp., Quadraspidiotus spp.,Rancora spp., Raphia spp., Reticultermes spp., Retinia spp., Rhagoletisspp, Rhagoletis pomonella, Rhipicephalus spp., Rhizoglyphus spp.,Rhizopertha spp., Rhodnius spp., Rhophalosiphum spp., Rhopobota spp.,Rhyacia spp., Rhyacionia spp., Rhynchopacha spp., Rhyzosthenes spp.,Rivula spp., Rondotia spp., Rusidrina spp., Rynchaglaea spp., Sabulodesspp., Sahlbergella spp., Sahlbergella singularis, Saissetia spp., Samiaspp., Sannina spp., Sanninoidea spp., Saphoideus spp., Sarcoptes spp.,Sathrobrota spp., Scarabeidae, Sceliodes spp., Schinia spp.,Schistocerca spp., Schizaphis spp., Schizura spp., Schreckensteiniaspp., Sciara spp., Scirpophaga spp., Scirthrips auranti, Scoparia spp.,Scopula spp., Scotia spp., Scotinophara spp., Scotogramma spp.,Scrobipalpa spp., Scrobipalpopsis spp., Semiothisa spp., Sereda spp.,Sesamia spp., Sesia spp., Sicya spp., Sideridis spp., Simyra spp.,Sineugraphe spp., Sitochroa spp., Sitobion spp., Sitophilus spp.,Sitotroga spp., Solenopsis spp., Smerinthus spp., Sophronia spp.,Spaelotis spp., Spargaloma spp., Sparganothis spp., Spatalistis spp.,Sperchia spp., Sphecia spp., Sphinx spp., Spilonota spp., Spodopteraspp., Spodoptera littoralis, Stagmatophora spp., Staphylinochrous spp.,Stathmopoda spp., Stenodes spp., Sterrha spp., Stomoxys spp., Strophedraspp., Sunira spp., Sutyna spp., Swammerdamia spp., Syllomatia spp.,Sympistis spp., Synanthedon spp., Synaxis spp., Syncopacma spp.,Syndemis spp., Syngrapha spp., Synthomeida spp., Tabanus spp.,Taeniarchis spp., Taeniothrips spp., Tannia spp., Tarsonemus spp.,Tegulifera spp., Tehama spp., Telejodes spp., Telorta spp., Tenebriospp., Tephhrina spp., Teratoglaea spp., Terricula spp., Tethea spp.,Tetranychus spp., Thalpophila spp., Thaumetopoea spp., Thiodia spp.,Thrips spp., Thrips palmi, Thrips tabaci, Thyridopteryx spp., Thyrisspp., Tineola spp., Tipula spp., Tortricidia spp., Tortrix spp., Tracheaspp., Trialeurodes spp., Trialeurodes vaporariorum, Triatoma spp.,Triaxomera spp., Tribolium spp., Tricodectes spp., Trichoplusia spp.,Trichoplusia ni, Trichoptilus spp., Trioza spp., Trioza erytreae,Triphaenia spp., Triphosa spp., Trogoderma spp., Tyria spp., Udea spp.,Uaspis spp., Unaspis citri, Utetheisa spp., Valeriodes spp., Vespa spp.,Vespamima spp., Vitacea spp., Vitula spp., Witlesia spp., Xanthia spp.,Xanthorhoe spp., Xanthotype spp., Xenomicta spp., Xenopsylla spp.,Xenopsylla cheopsis, Xestia spp., Xylena spp., Xylomyges spp., Xyrosarisspp., Yponomeuta spp., Ypsolopha spp., Zale spp., Zanclognathus spp.,Zeiraphera spp., Zenodoxus spp., Zeuzera spp., Zygaena spp.,

It is also possible to control pests of the class Nematoda using thecompounds according to the invention. Such pests include, for example,

root knot nematodes, cyst-forming nematodes and also stem and leafnematodes;

especially of Heterodera spp., e.g. Heterodera schachtii, Heterodoraavenae and Heterodora trifolii; Globodera spp., e.g. Globoderarostochiensis; Meloidogyne spp., e.g. Meloidogyne incognita andMeloidogyne javanica; Radopholus spp., e.g. Radopholus similis;Pratylenchus, e.g. Pratylenchus neglectans and Pratylenchus penetrans;Tylenchulus, e.g. Tylenchulus semipenetrans; Longidorus, Trichodorus,Xiphinema, Ditylenchus, Apheenchoides and Anguina; especiallyMeloidogyne, e.g. Meloidogyne incognita, and Heterodera, e.g. Heteroderaglycines.

An especially important aspect of the present invention is the use ofthe compounds of formula (I) according to the invention in theprotection of plants against parasitic feeding pests.

The action of the compounds according to the invention and thecompositions comprising them against animal pests can be significantlybroadened and adapted to the given circumstances by the addition ofother insecticides, acaricides or nematicides. Suitable additivesinclude, for example, representatives of the following classes of activeingredient: organophosphorus compounds, nitrophenols and derivatives,formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons,neonicotinoids and Bacillus thuringiensis preparations.

Examples of especially suitable mixing partners include: azamethiphos;chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine;diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil;fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos; kinoprene;lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon;profenofos; diofenolan; a compound obtainable from the Bacillusthuringiensis strain GC91 or from strain NCTC11821; pymetrozine;bromopropylate; methoprene; disulfoton; quinalphos; tau-fluvalinate;thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb;bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap;chlorfluazuron; chlorpyrifos; clothianidin; cyfluthrin;lambda-cyhalothrin; alpha-cypermethrin; zeta-cypermethrin; deltamethrin;diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenobucarb;fenvalerate; formothion; methiocarb; heptenophos; imidacloprid;isoprocarb; methamidophos; methomyl; mevinphos; parathion;parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron;terbufos; triazamate; fenobucarb; tebufenozide; fipronil;beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin;pyriproxyfen; pyrimidifen; nitenpyram; acetamiprid; emamectin;emamectin-benzoate; spinosad; a plant extract that is active againstinsects; a preparation that comprises nematodes and is active againstinsects; a preparation obtainable from Bacillus subtilis; a preparationthat comprises fungi and is active against insects; a preparation thatcomprises viruses and is active against insects; chlorfenapyr; acephate;acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541; azinphos A;azinphos M; azocyclotin; bendiocarb; bensultap; beta-cyfluthrin; BPMC;brofenprox; bromophos A; bufencarb; butocarboxin; butylpyridaben;cadusafos; carbaryl; carbophenothion; chloethocarb; chlorethoxyfos;chlormephos; cis-resmethrin; clocythrin; clofentezine; cyanophos;cycloprothrin; cyhexatin; demeton M; demeton S; demeton-S-methyl;dichlofenthion; dicliphos; diethion; dimethoate; dimethylvinphos;dioxathion; edifenphos; esfenvalerate; ethion; ethofenprox; ethoprophos;etrimphos; fenamiphos; fenbutatin oxide; fenothiocarb; fenpropathrin;fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate;flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH;hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofenphos; isoxathion;ivermectin; malathion; mecarbam; mesulfenphos; metaldehyde; metolcarb;milbemectin; moxidectin; naled; NC 184; nithiazine; omethoate; oxamyl;oxydemethon M; oxydeprofos; permethrin; phenthoate; phorate; phosmet;phoxim; pirimiphos M; pirimiphos E; promecarb; propaphos; prothiofos;prothoate; pyrachlophos; pyradaphenthion; pyresmethrin; pyrethrum;tebufenozide; salithion; sebufos; sulfotep; sulprofos; tebufenpyrad;tebupirimphos; tefluthrin; temephos; terbam; tetrachlorvinphos;thiacloprid; thiafenox; thiamethoxam; thiodicarb; thiofanox; thionazin;thuringiensin; tralomethrin; triarathene; triazophos; triazuron;trichlorfon; triflumuron; trimethacarb; vamidothion; xylylcarb; YI5301/5302; zetamethrin; DPX-MP062—indoxacarb; methoxyfenozide;bifenazate; XMC (3,5-xylyl methylcarbamate); or the fungus pathogenMetarhizium anisopliae.

The compounds according to the invention can be used to control, i.e. toinhibit or destroy, pests of the mentioned type occurring on plants,especially on useful plants and ornamentals in agriculture, inhorticulture and in forestry, or on parts of such plants, such as thefruits, blossoms, leaves, stems, tubers or roots, while in some casesplant parts that grow later are still protected against those pests.

Target crops include especially cereals, such as wheat, barley, rye,oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet;fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears,plums, peaches, almonds, cherries and berries, e.g. strawberries,raspberries and blackberries; leguminous plants, such as beans, lentils,peas and soybeans; oil plants, such as rape, mustard, poppy, olives,sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae,such as marrows, cucumbers and melons; fibre plants, such as cotton,flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruitand mandarins; vegetables, such as spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae,such as avocado, cinnamon and camphor; and tobacco, nuts, coffee,aubergines, sugar cane, tea, pepper, vines, hops, bananas, naturalrubber plants and ornamentals.

Further areas of use of the compounds according to the invention are theprotection of stored goods and storerooms and the protection of rawmaterials, and also in the hygiene sector, especially the protection ofdomestic animals and productive livestock against pests of the mentionedtype, more especially the protection of domestic animals, especiallycats and dogs, from infestation by fleas, ticks and nematodes.

The invention therefore relates also to pesticidal compositions, such asemulsifiable concentrates, suspension concentrates, directly sprayableor dilutable solutions, spreadable pastes, dilute emulsions, wettablepowders, soluble powders, dispersible powders, wettable powders, dusts,granules and encapsulations of polymer substances, that comprise atleast one of the compounds according to the invention, the choice offormulation being made in accordance with the intended objectives andthe prevailing circumstances.

The active ingredient is used in those compositions in pure form, asolid active ingredient, for example, in a specific particle size, orpreferably together with at least one of the adjuvants customary informulation technology, such as extenders, e.g. solvents or solidcarriers, or surface-active compounds (surfactants). In the area ofparasite control in humans, domestic animals, productive livestock andpets it will be self-evident that only physiologically tolerableadditives are used.

Solvents are, for example: non-hydrogenated or partly hydrogenatedaromatic hydrocarbons, preferably fractions C₈ to C₁₂ of alkylbenzenes,such as xylene mixtures, alkylated naphthalenes ortetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such asparaffins or cyclohexane, alcohols, such as ethanol, propanol orbutanol, glycols and ethers and esters thereof, such as propyleneglycol, dipropylene glycol ether, ethylene glycol or ethylene glycolmonomethyl or -ethyl ether, ketones, such as cyclohexanone, isophoroneor diacetone alcohol, strongly polar solvents, such asN-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide,water, non-epoxidized or epoxidized plant oils, such as non-epoxidizedor epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.

The solid carriers used, for example for dusts and dispersible powders,are as a rule natural rock powders, such as calcite, talc, kaolin,montmorillonite or attapulgite. Highly disperse silicic acids or highlydisperse absorbent polymers can also be added to improve the physicalproperties. Granular adsorptive granule carriers are porous types, suchas pumice, crushed brick, sepiolite or bentonite, and non-sorbentcarrier materials are calcite or sand. A large number of granularmaterials of inorganic or organic nature can furthermore be used, inparticular dolomite or comminuted plant residues.

Surface-active compounds are, depending on the nature of the activecompound to be formulated, nonionic, cationic and/or anionic surfactantsor surfactant mixtures with good emulsifying, dispersing and wettingproperties. The surfactants listed below are to be regarded only asexamples; many other surfactants which are customary in formulationtechnology and are suitable according to the invention are described inthe relevant literature.

Nonionic surfactants are, in particular, polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, which can contain 3 to 30 glycol ether groupsand 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to18 carbon atoms in the alkyl radical of the alkylphenols. Substanceswhich are furthermore suitable are water-soluble polyethylene oxideadducts, containing 20 to 250 ethylene glycol ether and 10 to 100propylene glycol ether groups, on propylene glycol, ethylenediaminopolypropylene glycol and alkyl polypropylene glycol having 1 to10 carbon atoms in the alkyl chain. The compounds mentioned usuallycontain 1 to 5 ethylene glycol units per propylene glycol unit. Examplesare nonylphenol-polyethoxyethanols, castor oil polyglycol ethers,polypropylene-polyethylene oxide adducts,tributylphenoxypoly-ethoxyethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol. Other substances are fatty acid esters ofpolyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are, in particular, quaternary ammonium saltswhich contain, as substituents, at least one alkyl radical having 8 to22 C atoms and, as further substituents, lower, non-halogenated orhalogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts arepreferably in the form of halides, methyl-sulfates or ethyl-sulfates.Examples are stearyl-trimethyl-ammonium chloride andbenzyl-di-(2-chloroethyl)-ethyl-ammonium bromide.

Suitable anionic surfactants can be both water-soluble soaps andwater-soluble synthetic surface-active compounds. Suitable soaps are thealkali metal, alkaline earth metal and substituted or unsubstitutedammonium salts of higher fatty acids (C₁₀-C₂₂), such as the sodium orpotassium salts of oleic or stearic acid, or of naturally occurringfatty acid mixtures, which can be obtained, for example, from coconutoil or tall oil; and furthermore also the fatty acid methyl-taurinesalts. However, synthetic surfactants are more frequently used, inparticular fatty sulfonates, fatty sulfates, sulfonated benzimidazolederivatives or alkylarylsulfonates. The fatty sulfonates and sulfatesare as a rule in the form of alkali metal, alkaline earth metal orsubstituted or unsubstituted ammonium salts and in general have an alkylradical of 8 to 22 C atoms, alkyl also including the alkyl moiety ofacyl radicals; examples are the sodium or calcium salt of ligninsulfonicacid, of dodecylsulfuric acid ester or of a fatty alcohol sulfatemixture prepared from naturally occurring fatty acids. These alsoinclude the salts of sulfuric acid esters and sulfonic acids of fattyalcohol-ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and a fatty acid radicalhaving about 8 to 22 C atoms. Alkylarylsulfonates are, for example, thesodium, calcium or triethanolammonium salts of dodecylbenzenesulfonicacid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonicacid-formaldehyde condensation product. Corresponding phosphates, suchas salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethyleneoxide adduct or phospholipids, can further also be used.

The compositions as a rule comprise 0.1 to 99%, in particular 0.1 to95%, of active compound and 1 to 99.9%, in particular 5 to 99.9%, of—atleast—one solid or liquid auxiliary, it being possible as a rule for 0to 25%, in particular 0.1 to 20%, of the composition to be surfactants(% is in each case per cent by weight). While concentrated compositionsare more preferred as commercial goods, the end user as a rule usesdilute compositions which comprise considerably lower concentrations ofactive compound. Preferred compositions are composed, in particular, asfollows (%=per cent by weight):

Emulsifiable Concentrates:

active ingredient: 1 to 90%, preferably 5 to 20%

surfactant: 1 to 30%, preferably 10 to 20%

solvent: 5 to 98%, preferably 70 to 85%

Dusts:

active ingredient: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension Concentrates:

active ingredient: 5 to 75%, preferably 10 to 50%

water: 94 to 24%, preferably 88 to 30%

surfactant: 1 to 40%, preferably 2 to 30%

Wettable Powders:

active ingredient: 0.5 to 90%, preferably 1 to 80%

surfactant: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 99%, preferably 15 to 98%

Granules:

active ingredient: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5 to 70%, preferably 97 to 85%

The compositions according to the invention may also comprise furthersolid or liquid adjuvants, such as stabilisers, e.g. vegetable oils orepoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil orsoybean oil), antifoams, e.g. silicone oil, preservatives, viscosityregulators, binders and/or tackifiers as well as fertilisers or otheractive ingredients for obtaining special effects, e.g. acaricides,bactericides, fungicides, nematicides, molluscicides or selectiveherbicides.

The crop protection products according to the invention are prepared inknown manner, in the absence of adjuvants, e.g. by grinding, sievingand/or compressing a solid active ingredient or mixture of activeingredients, for example to a certain particle size, and in the presenceof at least one adjuvant, for example by intimately mixing and/orgrinding the active ingredient or mixture of active ingredients with theadjuvant(s). The invention relates likewise to those processes for thepreparation of the compositions according to the invention and to theuse of the compounds of formula (I) in the preparation of thosecompositions.

The invention relates also to the methods of application of the cropprotection products, i.e. the methods of controlling pests of thementioned type, such as spraying, atomising, dusting, coating, dressing,scattering or pouring, which are selected in accordance with theintended objectives and the prevailing circumstances, and to the use ofthe compositions for controlling pests of the mentioned type. Typicalrates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to500 ppm, of active ingredient. The rates of application per hectare aregenerally from 1 to 2000 g of active ingredient per hectare, especiallyfrom 10 to 1000 g/ha, preferably from 20 to 600 g/ha.

A preferred method of application in the area of crop protection isapplication to the foliage of the plants (foliar application), thefrequency and the rate of application being dependent upon the risk ofinfestation by the pest in question. However, the active ingredient canalso penetrate the plants through the roots (systemic action) when thelocus of the plants is impregnated with a liquid formulation or when theactive ingredient is incorporated in solid form into the locus of theplants, for example into the soil, e.g. in granular form (soilapplication). In the case of paddy rice crops, such granules may beapplied in metered amounts to the flooded rice field.

The crop protection products according to the invention are alsosuitable for protecting plant propagation material, e.g. seed, such asfruits, tubers or grains, or plant cuttings, against animal pests. Thepropagation material can be treated with the composition beforeplanting: seed, for example, can be dressed before being sown. Theactive ingredients according to the invention can also be applied tograins (coating), either by impregnating the seeds in a liquidformulation or by coating them with a solid formulation. The compositioncan also be applied to the planting site when the propagation materialis being planted, for example to the seed furrow during sowing. Theinvention relates also to such methods of treating plant propagationmaterial and to the plant propagation material so treated.

The following Examples serve to illustrate the invention. They do notlimit the invention. Temperatures are given in degrees Celsius; mixingratios of solvents are given in parts by volume.

PREPARATION EXAMPLES Example P1 Preparation of1-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-1H-pyrrole

P1.1: 2 g of methanesulfonic acid3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl ester, 1.14 gof 4-iodophenol and 1.96 g of potassium carbonate are stirred for 24hours at 50° C. in 20 ml of dimethylformamide. The reaction mixture ispoured onto water and extracted with ethyl acetate. The organic phase iswashed with water and potassium carbonate solution and concentrated.Purification over silica gel yields1,3-dichloro-5-(3,3-dichloro-allyloxy)-2-[3-(4-iodo-phenoxy)-propoxy]-benzene.¹H-NMR (CDCl₃) 300 MHz: 2.28 (m, 2H), 4.13 (t, 2H), 4.22 (t, 2H), 4.58(d, 2H), 6.10 (t, 1H), 6.71 (d, 2H), 6.81 (s, 2H), 7.55 (d, 2H)

P1.2: 200 mg of1,3-dichloro-5-(3,3-dichloro-allyloxy)-2-[3-(4-iodo-phenoxy)-propoxy]-benzene,29 mg of pyrrole, 6.9 mg of copper(I) iodide, 2.2 mg of ethylenediamineand 155 mg of potassium triphosphate are stirred for 24 hours at 110° C.in 4 ml of dioxane. The reaction mixture is diluted with ethyl acetateand filtered. Concentration and purification over silica gel yield thetitle compound (compound 1.1).

Example P2 Preparation of5-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-2H-tetrazoleand5-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]propoxy}-phenyl)-2-ethyl-2H-tetrazole

P2.1: 3 g of methanesulfonic acid3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl ester, 0.93 gof 4-hydroxybenzonitrile and 2.9 g of potassium carbonate are stirredfor 17 hours at 40° C. in 30 ml of dimethylformamide. The reactionmixture is poured onto water and extracted with ethyl acetate.Concentration of the organic phase yields4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-benzonitrile.¹H-NMR (CDCl₃) 300 MHz: 2.30 (m, 2H), 4.14 (t, 2H), 4.32 (t, 2H), 4.58(d, 2H), 6.10 (t, 1H), 6.83 (s, 2H), 7.00 (d, 2H), 7.60 (d, 2H)

P2.2: 2 g of4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-benzonitrile,1.2 g of ammonium chloride and 1.5 g of sodium azide are stirred for 48hours at 100° C. in 50 ml of dimethylformamide. The reaction mixture ispoured onto cold dilute hydrochloric acid and extracted with ethylacetate. Concentration of the organic phase and crystallisation fromdiethyl ether/hexane yield5-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-2H-tetrazolehaving a melting point of 159-161° C.

P2.3: 100 mg of5-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-2H-tetrazole,48 mg of ethyl iodide and 141 mg of potassium carbonate are stirred for4 hours at 50° C. in 3 ml of dimethylformamide. The reaction mixture ispoured onto water and extracted with ethyl acetate. Concentration of theorganic phase and purification over silica gel yield5-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-2-ethyl-2H-tetrazole(compound 1.4).

Example P3 Preparation of3-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-5-methyl-[1,2,4]oxadiazole

P3.1: 1.1 g of4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-benzonitrile,247 mg of hydroxylamine hydrochloride and 430 mg of triethylamine arestirred for 48 hours at 80° C. in 25 ml of ethanol. The reaction mixtureis poured onto water and extracted with ethyl acetate. Concentration ofthe organic phase and crystallisation from diethyl ether yield4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-N-hydroxy-benzamidinehaving a melting point of 144-146° C.

P3.2: 100 mg of4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-N-hydroxybenzamidineare placed in 2 ml of toluene. 20 mg of acetyl chloride and 2 ml ofpyridine are added, and heating is carried out for 4 hours at 120° C.The reaction mixture is concentrated, and the residue is taken up inethyl acetate and washed with dilute hydrochloric acid and water.Concentration of the organic phase and purification over silica gelyield the title compound (compound 1.10).

Example P4 Preparation of5-chloro-3-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-isoxazole

P4.1: 307 mg of tert-butyl hypochloride in 5 ml of carbon tetrachlorideare added dropwise over a period of 10 minutes, at 20-30° C., to 1.3 gof4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-N-hydroxy-benzimidein 15 ml of carbon tetrachloride. After 3 hours at room temperature, thereaction mixture is washed with water and concentrated. Crystallisationfrom hexane yields4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phen-oxy]-propoxy}-N-hydroxy-benzimidoylchloride.

P4.2: 150 mg of4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-N-hydroxy-benzimidoylchloride are placed in 1 ml of 1,1-dichloroethane at 0° C., and asolution of 76 mg of triethylamine in 1 ml of 1,1-dichloroethane isadded dropwise thereto over a period of one hour. After one hour at 0°C. and 18 hours at 25° C., the reaction mixture is poured onto water andextracted with ethyl acetate. Concentration and purification over silicagel yield the title compound (compound 1.17).

Example P5 Preparation of1-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-5-isopropylsulfanyl-1H-tetrazole

P5.1: 388 mg of 4-(5-mercapto-tetrazol-1-yl)-phenol, 430 mg of isopropyliodide and 168 mg of sodium hydrogen carbonate are stirred for 5 hoursat 80° C. in 4 ml of acetonitrile. The reaction mixture is diluted withethyl acetate, washed with sodium hydrogen carbonate solution and water,and concentrated. 4-(5-lsopropylsulfanyl-tetrazol-1-yl)-phenol isobtained in that manner. ¹H-NMR [(CD₃)₂SO] 300 MHz: 1.38 (d, 6H), 3.78(m, 1H), 6.80 (d, 2H), 7.25 (d, 2H), 10.08 (s, 1H).

P5.2: 400 mg of 4-(5-isopropylsulfanyl-tetrazol-1-yl)-phenol, 471 mg ofbromopropanol, 473 mg of potassium carbonate and 10 mg of potassiumiodide are stirred for 15 hours at reflux in 10 ml of acetone. Thereaction mixture is filtered and concentrated. The residue is taken upin ethyl acetate, washed with water and concentrated. Purification oversilica gel yields3-[4-(5-isopropylsulfanyl-tetrazol-1-yl)-phenoxy]-propan-1-ol. ¹H-NMR(CDCl₃) 300 MHz: 1.50 (d, 6H), 2.09 (m, 2H), 3.90 (t, 2H), 4.12 (m, 1H),4.19 (t, 2H), 7.03 (d, 2H), 7.43 (d, 2H)

P5.3: 1.41 g of azodicarboxylic acid diisopropyl ester are added at 0°C. to 1.83 g of triphenylphosphine in 30 ml of THF. After 30 minutes, asolution of 1.96 g of3-[4-(5-isso-propylsulfanyl-tetrazol-1-yl)-phenoxy]-propan-1-ol and 1.88g of benzoic acid 3,5-dichloro-4-hydroxy-phenyl ester in 30 ml of THF isadded dropwise. After one hour at 0° C. and 24 hours at roomtemperature, the reaction mixture is concentrated. Purification oversilica gel yields benzoic acid3,5-dichloro-4-{3-[4-(5-isopropylsulfanyl-tetrazol-1-yl)-phenoxy]-propoxy}-phenylester. ¹H-NMR (CDCl₃) 300 MHz: 1.50 (d, 2H), 2.33 (m, 2H), 4.26 (t, 2H),4.38 (t, 2H), 4.99 (m, 1H), 7.09 (d, 2H), 7.23 (s, 2H), 7.42-7.70 (m,5H), 8.15 (d, 2H)

P5.4: 3.5 ml of n-butylamine are added dropwise at 0-5° C. to a solutionof 2 g of benzoic acid3,5-dichloro-4-{3-[4-(5-isopropylsulfanyl-tetrazol-1-yl)-phenoxy]-propoxy}-phenylester. After 30 minutes at 0-5° C. and one hour at room temperature, thereaction mixture is concentrated. Purification over silica gel yields3,5-dichloro-4-{3-[4-(5-isopropylsulfanyl-tetrazol-1-yl)-phenoxy]-propoxy}-phenol.¹H-NMR (CDCl₃) 300 MHz: 1.50 (d, 2H), 2.32 (m, 2H), 4.08-4.20 (m, 3H),4.35 (t, 2H), 5.62 (s, 1H), 6.82 (s, 2H), 7.09 (d, 2H), 7.45 (d, 2H)

P5.5: 900 mg of3,5-dichloro-4-{3-[4-(5-isopropylsulfanyl-tetrazol-1-yl)-phenoxy]-propoxy}-phenol,720 mg of 1,1,1,3-tetrachloropropane, 691 mg of potassium carbonate and10 mg of potassium iodide are stirred for 48 hours at 60° C. in 30 ml ofacetone. The reaction mixture is filtered and the filtrate isconcentrated. Purification over silica gel yields the title compound(compound 1.20).

Example P6 Preparation of3-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-4H-[1,2,4]oxadiazol-5-one

90 mg of chloroformic acid ethyl ester in 1 ml of acetone are addeddropwise at 5° C. to 400 mg of4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-N-hydroxy-benzamidineand 127 mg of potassium carbonate in 3 ml of acetone. After 3 hours at0-5° C., the reaction mixture is poured onto water and extracted withdichloromethane. Concentration of the organic phase and purificationover silica gel yield the title compound (compound 1.15).

Example P7 Preparation of5-chloro-3-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-[1,2,4]oxadiazole

90 mg of3-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-4H-[1,2,4]oxadiazol-5-one,14 mg of pyridine and 0.2 ml of phosphorus oxychloride are stirred for14 hours at 130° C. The reaction mixture is poured onto ice-water andextracted with ethyl acetate. Concentration of the organic phase andpurification over silica gel yield the title compound (compound 1.16).

Example P8 Preparation of3-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-[1,2,4]oxadiazole

150 mg of4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-N-hydroxy-benzamidineand 15 mg of boron trifluoride ethyl etherate are stirred for 2 hours at140° C. in 2 ml of triethyl orthoformate. The reaction mixture isconcentrated, and the residue is taken up in ethyl acetate and washedwith water. Concentration of the organic phase and purification oversilica gel yield the title compound (compound 1.14).

Example P9 Preparation of2-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-4-methyl-thiazole

P9.1: Preparation of 4-(4-methyl-thiazol-2-yl)-phenol. 200 mg of4-hydroxy-thiobenz-amide and 144 mg of chloroacetone are stirred for 17hours at room temperature and for 24 hours at 80° C. in 2 ml of ethanol.The reaction mixture is concentrated completely. The title compound soobtained is reacted further in the form of the crude product.

P9.2: 96 mg of 4-(4-methyl-thiazol-2-yl)-phenol, 212 mg ofmethanesulfonic acid3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl ester and 207mg of potassium carbonate are stirred for 24 hours at 50° C. in 3 ml ofdimethylformamide. The reaction mixture is poured onto water andextracted with ethyl acetate. Concentration of the organic phase andpurification over silica gel yield the title compound (compound 1.23).

Example P10 Preparation of1-(4-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propoxy}-phenyl)-1H-[1,2,4]triazole

125 mg of 4-[1,2,4]triazol-1-yl-phenol, 212 mg of methanesulfonic acid3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl ester and 207mg of potassium carbonate are stirred for 24 hours at 50° C. in 4 ml ofdimethylformamide. The reaction mixture is poured onto water andextracted with ethyl acetate. Concentration of the organic phase andpurification over silica gel yield the title compound (compound 1.9).

Example P11

In a manner analogous to that described above it is also possible toprepare the further compounds of the following Tables. The bond givenwith the symbol in the said tables indicates the connection of thesubstituent E with the remainder of the chemical structure.

TABLE 1 Compounds of formula (Ia)

No. E ¹H-NMR (CDCl₃) 300 MHz 1.1

2.30(m, 2H), 4.16(t, 2H), 4.28(t, 2H), 4.59(d, 2H) 6.10(t, 1H), 6.31(s,2H), 6.82(s, 2H), 6.93–7.01 (d+s, 4H), 7.30(d, 2H) 1.2

Solvent(CD₃)₂SO: 2.24(m, 2H), 4.12(t, 2H), 4.31(t, 2H), 4.70(d, 2H),6.50(t, 1H), 7.17(s, 2H), 7.20(d, 2H), 7.98(d, 2H) 1.3

2.32(m, 2H), 4.18(t, 2H), 4.33(t, 2H), 4.39(s, 3H), 4.58(d, 2H), 6.11(t,1H), 6.82(s, 2H), 7.03(d, 2H), 8.07(d, 2H) 1.4

1.69(t, 3H), 2.32(m, 2H), 4.18(t, 2H), 4.32(t, 2H), 4.58(d, 2H), 4.68(q,2H), 6.10(t, 1H), 6.82(s, 2H), 7.03(d, 2H), 8.08(d, 2H) 1.5

1.00(t, 3H), 2.10(m, 2H), 2.32(m, 2H), 4.18(t, 2H), 4.32(t, 2H),4.53–4.67(m, 4H), 6.10(t, 1H), 6.82(s, 2H), 7.03(d, 2H), 8.08(d, 2H) 1.6

1.00(d, 6H), 2.23–2.53(m, 3H), 4.18(t, 2H), 4.32(t, 2H), 4.43(d2H),4.58(d, 2H), 6.11(t, 1H), 6.82(s, 2H), 7.03(d, 2H), 8.08(d, 2H) 1.7

1.00(d, 6H), 1.53–1.71(m1H), 1.96(m, 2H), 2.32(m, 2H), 4.18(t, 2H),4.33(t, 2H), 4.58(d, 2H), 4.65(t, 2H), 6.11(t, 1H), 6.82(s, 2H), 7.03(d,2H), 8.08(d, 2H) 1.8

0.89(t, 3H), 1.20–1.43(m, 6H), 1.93–2.12(m, 2H), 2.32(m, 2H), 4.18(t,2H), 4.33(t, 2H), 4.52–4.69(m, 4H), 6.11(t, 1H), 6.82(s, 2H), 7.03(d,2H), 8.08(d, 2H) 1.9

2.31(m, 2H), 4.17(t, 2H), 4.31(t, 2H), 4.59(d, 2H), 6.11(t, 1H), 6.83(s,2H), 7.04(d, 2H), 7.58(d, 2H), 8.08(s, 1H), 8.45(s, 1H) 1.10

2.32(m, 2H), 2.62(s, 3H), 4.18(t, 2H), 4.32(t, 2H), 4.59(d, 2H), 6.10(t,1H), 6.82(s, 2H), 7.01(d, 2H), 8.00(d, 2H) 1.11

1.42(t, 3H), 2.30(m, 2H), 2.97(q, 2H), 4.18(t, 2H), 4.32(t, 2H), 4.58(d,2H), 6.10(t, 1H), 6.82(s, 2H), 7.01(d, 2H), 8.00(d, 2H) 1.12

1.13–1.36(m, 4H), 2.17–2.38(m, 4H), 4.18(t, 2H), 4.32(t, 2H), 4.58(d,2H), 6.12(t, 1H), 6.82(s, 2H), 7.00(d, 2H), 7.98(d, 2H) 1.13

2.32(m, 2H), 4.19(t, 2H), 4.35(t, 2H), 4.58(d, 2H), 6.10(t, 1H), 6.83(s,2H), 7.06(d, 2H), 8.06(d, 2H) 1.14

2.32(m, 2H), 4.18(t, 2H), 4.33(t, 2H), 4.58(d, 2H), 6.10(t, 1H), 6.83(s,2H), 7.03(d, 2H), 8.07(d, 2H), 8.70(s, 1H) 1.15

Solvent(CD₃)₂SO: 2.12(m, 2H), 4.00(t, 2H), 4.20(t, 2H), 4.59(d, 2H),6.48(t, 1H), 7.02–7.10(s+d, 4H), 7.67(d, 2H), 12.30–12.95(s, 1H) 1.16

2.31(m, 2H), 4.18(t, 2H), 4.32(t, 2H), 4.58(d, 2H), 6.10(t, 1H), 6.82(s,2H), 7.02(d, 2H), 7.98(d, 2H) 1.17

2.32(m, 2H), 4.18(t, 2H), 4.31(t, 2H), 4.59(d, 2H), 6.10(t, 1H), 6.42(s,1H), 6.82(s, 2H), 7.00(d, 2H), 7.70(d, 2H) 1.18

2.32(m, 2H), 2.83(s, 3H), 4.18(t, 2H), 4.37(t, 2H), 4.60(d, 2H), 6.12(t,1H), 6.83(s, 2H), 7.09(d, 2H), 7.47(d, 2H) 1.19

1.50(t, 3H), 2.32(m, 2H), 3.49(q, 2H), 4.18(t, 2H), 4.35(t, 2H), 4.59(d,2H), 6.11(t, 1H), 6.83(s, 2H), 7.08(d, 2H), 7.47(d, 2H) 1.20

1.50(d, 6H), 2.32(m, 2H), 4.08–4.20(m, 4H), 4.33(t, 2H), 4.59(d, 2H),6.11(t, 1H), 6.83(s, 2H), 7.08(d, 2H), 7.47(d, 2H) 1.21

0.38(m, 2H), 0.68(m, 2H), 1.28(m, 1H), 2.32(m, 2H), 3.45(d, 2H), 4.19(t,2H), 4.33(t, 2H), 4.59(d, 2H), 6.11(t, 1H), 6.83(s, 2H), 7.08(d, 2H),7.48(d, 2H) 1.22

2.33(m, 2H), 4.00(t, 2H), 4.35(t, 2H), 4.59(d, 2H), 5.21(d, 1H), 5.39(d,1H), 5.92–6.07(m, 1H), 6.10(t, 1H), 6.83(s, 2H), 7.09(d, 2H), 7.47(d,2H) 1.23

2.30(m, 2H), 2.50(s, 3H), 4.17(t, 2H), 4.30(t, 2H), 4.59(d, 2H), 6.10(t,1H), 6.80(s, 1H), 6.82(s, 2H), 6.98(d, 2H), 7.88(d, 2H) 1.24

1.25

1.26

1.27

1.28

1.29

1.30

1.31

1.32

1.33

1.34

1.35

1.36

1.37

1.38

1.39

1.40

1.41

1.42

1.43

1.44

1.45

1.46

1.47

1.48

1.49

1.50

1.51

1.52

1.53

1.54

1.55

1.56

1.57

1.58

2.20–2.40(m, 8H), 4.15(t, 2H), 4.35(t, 2H), 4.59(d, 2H), 5.95(s, 1H),6.10(t, 1H), 6.80(s, 2H), 6.95(d, 2H), 7.35(d, 2H) 1.59

2.2–2.4(m, 5H), 4.15(t, 2H), 4.35(t, 2H), 4.59(d, 2H), 6.10(t, 1H),6.40(s, 1H), 6.80(s, 2H), 7.00(d, 2H), 7.35(d, 2H) 1.60

2.20–2.40(m, 5H), 4.15(t, 2H), 4.35(t, 2H), 4.59(d, 2H), 6.10(t, 1H),6.55(s, 1H), 6.80(s, 2H), 6.95(d, 2H), 7.35(d, 2H) 1.61

1.62

1.63

1.64

1.65

1.66

1.67

1.68

1.69

1.70

1.71

1.72

1.73

1.74

1.75

1.76

1.77

TABLE A Compounds of formulae

No. X₁ X₂ R₁₀ A.1 Cl Cl H A.2 Cl Cl CN A.3 Cl Cl Cl A.4 Cl Cl Br A.5 ClCl CH₃ A.6 Cl Cl C₂H₅ A.7 Cl Cl n-C₃H₇ A.8 Cl Cl n-C₄H₉ A.9 Cl Cln-C₅H₁₁ A.10 Cl Cl n-C₆H₁₃ A.11 Cl Cl iso-C₃H₇ A.12 Cl Cl iso-C₄H₉ A.13Cl Cl iso-C₅H₁₁ A.14 Cl Cl tert-C₄H₉ A.15 Cl Cl CH₂C(CH₃)₃ A.16 Cl Clc-propyl A.17 Cl Cl CH₂(c-propyl) A.18 Cl Cl CF₃ A.19 Cl Cl CH₂CF₃ A.20Cl Cl CH₂CHF₂ A.21 Cl Cl CH₂CH₂F A.22 Cl Cl CH₂CH═CH₂ A.23 Cl Cl CH₂C≡CHA.24 Cl Cl CH₂C≡CCH₃ A.25 Cl Cl CH₂CH═CCl₂ A.26 Cl Cl OH A.27 Cl Cl OCH₃A.28 Cl Cl O—C₂H₅ A.29 Cl Cl O-n-C₃H₇ A.30 Cl Cl O-n-C₄H₉ A.31 Cl ClO-n-C₅H₁₁ A.32 Cl Cl O-n-C₆H₁₃ A.33 Cl Cl O-iso-C₃H₇ A.34 Cl ClO-iso-C₄H₉ A.35 Cl Cl O-iso-C₅H₁₁ A.36 Cl Cl O-tert-C₄H₉ A.37 Cl ClO-CH₂C(CH₃)₃ A.38 Cl Cl O-c-propyl A.39 Cl Cl O—CH₂(c-propyl) A.40 Cl ClO—CF₃ A.41 Cl Cl O—CH₂CF₃ A.42 Cl Cl O—CH₂CHF₂ A.43 Cl Cl O—CH₂CH₂F A.44Cl Cl O—CH₂CH═CH₂ A.45 Cl Cl O—CH₂C≡CH A.46 Cl Cl O—CH₂C≡CCH₃ A.47 Cl ClO—CH₂CH═CCl₂ A.48 Cl Cl SH A.A9 Cl Cl SCH₃ A.50 Cl Cl S—C₂H₅ A.51 Cl ClS-n-C₃H₇ A.52 Cl Cl S-n-C₄H₉ A.53 Cl Cl S-n-C₅H₁₁ A.54 Cl Cl S-n-C₆H₁₃A.55 Cl Cl S-iso-C₃H₇ A.56 Cl Cl S-iso-C₄H₉ A.57 Cl Cl S-iso-C₅H₁₁ A.58Cl Cl S-tert-C₄H₉ A.59 Cl Cl S-CH₂C(CH₃)₃ A.60 Cl Cl S-c-propyl A.61 ClCl S—CH₂(c-propyl) A.62 Cl Cl S—CF₃ A.63 Cl Cl S—CH₂CF₃ A.64 Cl ClS—CH₂CHF₂ A.65 Cl Cl S—CH₂CH₂F A.66 Cl Cl S—CH₂CH═CH₂ A.67 Cl ClS—CH₂C≡CH A.68 Cl Cl S—CH₂C≡CCH₃ A.69 Cl Cl S—CH₂CH═CCl₂ A.70 Cl ClCH₂OH A.71 Cl Cl CH₂OCH₃ A.72 Cl Cl CH₂O—C₂H₅ A.73 Cl Cl CH₂O-n-C₃H₇A.74 Cl Cl CH₂O-n-C₄H₉ A.75 Cl Cl CH₂O-n-C₅H₁₁ A.76 Cl Cl CH₂O-n-C₆H₁₃A.77 Cl Cl CH₂O-iso-C₃H₇ A.78 Cl Cl CH₂O-iso-C₄H₉ A.79 Cl ClCH₂O-iso-C₅H₁₁ A.80 Cl Cl CH₂O-tert-C₄H₉ A.81 Cl Cl CH₂O—CH₂C(CH₃)₃ A.82Cl Cl CH₂O-c-propyl A.83 Cl Cl CH₂O—CH₂(c-propyl) A.84 Cl Cl CH₂O—CF₃A.85 Cl Cl CH₂O—CH₂CF₃ A.86 Cl Cl CH₂O—CH₂CHF₂ A.87 Cl Cl CH₂O—CH₂CH₂FA.88 Cl Cl CH₂O—CH₂CH═CH₂ A.89 Cl Cl CH₂O—CH₂C≡CH A.90 Cl ClCH₂O—CH₂C≡CCH₃ A.91 Cl Cl CH₂O—CH₂CH═CCl₂ A.92 Cl Cl C(═O)OH A.93 Cl ClC(═O)OCH₃ A.94 Cl Cl C(═O)O—C₂H₅ A.95 Cl Cl C(═O)O-n-C₃H₇ A.96 Cl ClC(═O)O-n-C₄H₉ A.97 Cl Cl C(═O)O-n-C₅H₁₁ A.98 Cl Cl C(═O)O-n-C₆H₁₃ A.99Cl Cl C(═O)O-iso-C₃H₇ A.100 Cl Cl C(═O)O-iso-C₄H₉ A.101 Cl ClC(═O)O-iso-C₅H₁₁ A.102 Cl Cl C(═O)O-tert-C₄H₉ A.103 Cl ClC(═O)O—CH₂C(CH₃)₃ A.104 Cl Cl C(═O)O-c-propyl A.105 Cl ClC(═O)O—CH₂(c-propyl) A.106 Cl Cl C(═O)O—CF₃ A.107 Cl Cl C(═O)O—CH₂CF₃A.108 Cl Cl C(═O)O—CH₂CHF₂ A.109 Cl Cl C(═O)O—CH₂CH₂F A.110 Cl ClC(═O)O—CH₂CH═CH₂ A.111 Cl Cl C(═O)O—CH₂C≡CH A.112 Cl Cl C(═O)O—CH₂C≡CCH₃A.113 Cl Cl C(═O)O—CH₂CH═CCl₂ A.114 Cl Cl C(═O)CH₃ A.115 Cl ClC(═O)—C₂H₅ A.116 Cl Cl C(═O)-n-C₃H₇ A.117 Cl Cl C(═O)-n-C₄H₉ A.118 Cl ClC(═O)-n-C₅H₁₁ A.119 Cl Cl C(═O)-n-C₆H₁₃ A.120 Cl Cl C(═O)-iso-C₃H₇ A.121Cl Cl C(═O)-iso-C₄H₉ A.122 Cl Cl C(═O)-iso-C₅H₁₁ A.123 Cl ClC(═O)-tert-C₄H₉ A.124 Cl Cl C(═O)—CH₂C(CH₃)₃ A.125 Cl Cl C(═O)-c-propylA.126 Cl Cl C(═O)—CH₂(c-propyl) A.127 Cl Cl C(═)—CF₃ A.128 Cl ClC(═O)—CH₂CF₃ A.129 Cl Cl C(═O)—CH₂CHF₂ A.130 Cl Cl C(═O)—CH₂CH₂F A.131Cl Cl C(═O)—CH₂CH═CH₂ A.132 Cl Cl C(═O)—CH₂C≡CH A.133 Cl ClC(═O)—CH₂C≡CCH₃ A.134 Cl Cl C(═O)—CH₂CH═CCl₂ A.135 Br Br H A.136 Br BrCN A.137 Br Br Cl A.138 Br Br Br A.139 Br Br CH₃ A.140 Br Br C₂H₅ A.141Br Br n-C₃H₇ A.142 Br Br n-C₄H₉ A.143 Br Br n-C₅H₁₁ A.144 Br Br n-C₆H₁₃A.145 Br Br iso-C₃H₇ A.146 Br Br iso-C₄H₉ A.147 Br Br iso-C₅H₁₁ A.148 BrBr tert-C₄H₉ A.149 Br Br CH₂C(CH₃)₃ A.150 Br Br c-propyl A.151 Br BrCH₂(c-propyl) A.152 Br Br CF₃ A.153 Br Br CH₂CF₃ A.154 Br Br CH₂CHF₂A.155 Br Br CH₂CH₂F A.156 Br Br CH₂CH═CH₂ A.157 Br Br CH₂C≡CH A.158 BrBr CH₂C≡CCH₃ A.159 Br Br CH₂CH═CCl₂ A.160 Br Br OH A.161 Br Br OCH₃A.162 Br Br O—C₂H₅ A.163 Br Br O-n-C₃H₇ A.164 Br Br O-n-C₄H₉ A.165 Br BrO-n-C₅H₁₁ A.166 Br Br O-n-C₆H₁₃ A.167 Br Br O-iso-C₃H₇ A.168 Br BrO-iso-C₄H₉ A.169 Br Br O-iso-C₅H₁₁ A.170 Br Br O-tert-C₄H₉ A.171 Br BrO—CH₂C(CH₃)₃ A.172 Br Br O-c-propyl A.173 Br Br O—CH₂(c-propyl) A.174 BrBr O—CF₃ A.175 Br Br O—CH₂CF₃ A.176 Br Br O—CH₂CHF₂ A.177 Br BrO—CH₂CH₂F A.178 Br Br O—CH₂CH═CH₂ A.179 Br Br O—CH₂C≡CH A.180 Br BrO—CH₂C≡CCH₃ A.181 Br Br O—CH₂CH═CCl₂ A.182 Br Br SH A.183 Br Br SCH₃A.184 Br Br S—C₂H₅ A.185 Br Br S-n-C₃H₇ A.186 Br Br S-n-C₄H₉ A.187 Br BrS-n-C₅H₁₁ A.188 Br Br S-n-C₆H₁₃ A.189 Br Br S-iso-C₃H₇ A.190 Br BrS-iso-C₄H₉ A.191 Br Br S-iso-C₅H₁₁ A.192 Br Br S-tert-C₄H₉ A.193 Br BrS—CH₂C(CH₃)₃ A.194 Br Br S-c-propyl A.195 Br Br S—CH₂(c-propyI) A.196 BrBr S—CF₃ A.197 Br Br S—CH₂CF₃ A.198 Br Br S—CH₂CHF₂ A.199 Br BrS—CH₂CH₂F A.200 Br Br S—CH₂CH═CH₂ A.201 Br Br S—CH₂C≡CH A.202 Br BrS—CH₂C≡CCH₃ A.203 Br Br S—CH₂CH═CCl₂ A.204 Br Br CH₂OH A.205 Br BrCH₂OCH₃ A.206 Br Br CH₂O—C₂H₅ A.207 Br Br CH₂O-n-C₃H₇ A.208 Br BrCH₂O-n-C₄H₉ A.209 Br Br CH₂O-n-C₅H₁₁ A.210 Br Br CH₂O-n-C₆H₁₃ A.211 BrBr CH₂O-iso-C₃H₇ A.212 Br Br CH₂O-iso-C₄H₉ A.213 Br Br CH₂O-iso-C₅H₁₁A.214 Br Br CH₂O-tert-C₄H₉ A.215 Br Br CH₂O—CH₂C(CH₃)₃ A.216 Br BrCH₂O-c-propyl A.217 Br Br CH₂O—CH₂(c-propyl) A.218 Br Br CH₂O—CF₃ A.219Br Br CH₂O—CH₂CF₃ A.220 Br Br CH₂O—CH₂CHF₂ A.221 Br Br CH₂O—CH₂CH₂FA.222 Br Br CH₂O—CH₂CH═CH₂ A.223 Br Br CH₂O—CH₂C≡CH A.224 Br BrCH₂O—CH₂C≡CCH₃ A.225 Br Br CH₂O—CH₂CH═CCl₂ A.226 Br Br C(═O)OH A.227 BrBr C(═O)OCH₃ A.228 Br Br C(═O)O—C₂H₅ A.229 Br Br C(═O)O-n-C₃H₇ A.230 BrBr C(═O)O-n-C₄H₉ A.231 Br Br C(═O)O-n-C₅H₁₁ A.232 Br Br C(═O)O-n-C₆H₁₃A.233 Br Br C(═O)O-iso-C₃H₇ A.234 Br Br C(═O)O-iso-C₄H₉ A.235 Br BrC(═O)O-iso-C₅H₁₁ A.236 Br Br C(═O)O-tert-C₄H₉ A.237 Br BrC(═O)O—CH₂C(CH₃)₃ A.238 Br Br C(═O)O-c-propyl A.239 Br BrC(═O)O—CH₂(c-propyl) A.240 Br Br C(═O)O—CF₃ A.241 Br Br C(═O)O—CH₂CF₃A.242 Br Br C(═O)O—CH₂CHF₂ A.243 Br Br C(═O)O—CH₂CH₂F A.244 Br BrC(═O)O—CH₂CH═CH₂ A.245 Br Br C(═O)O—CH₂C≡CH A.246 Br Br C(═O)O—CH₂C≡CCH₃A.247 Br Br C(═O)—CH₂CH═CCl₂ A.248 Br Br C(═O)CH₃ A.249 Br Br C(═O)—C₂H₅A.250 Br Br C(═O)-n-C₃H₇ A.251 Br Br C(═O)-n-C₄H₉ A.252 Br BrC(═O)-n-C₅H₁₁ A.253 Br Br C(═O)-n-C₆H₁₃ A.254 Br Br C(═O)-iso-C₃H₇ A.255Br Br C(═O)-iso-C₄H₉ A.256 Br Br C(═O)-iso-C₅H₁₁ A.257 Br BrC(═O)-tert-C₄H₉ A.258 Br Br C(═O)—CH₂C(CH₃)₃ A.259 Br Br C(═O)-c-propylA.260 Br Br C(═O)—CH₂(c-propyl) A.261 Br Br C(═O)—CF₃ A.262 Br BrC(═O)—CH₂CF₃ A.263 Br Br C(═O)—CH₂CHF₂ A.264 Br Br C(═O)—CH₂CH₂F A.265Br Br C(═O)—CH₂CH═CH₂ A.266 Br Br C(═O)—CH₂C≡CH A.267 Br BrC(═O)—CH₂C≡CCH₃ A.268 Br Br C(═O)—CH₂CH═CCl₂

Table 2: A compound of the general formula (Ib) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 3: A compound of the general formula (Ib) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 4: A compound of the general formula (Ib) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 5: A compound of the general formula (Ib) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 6: A compound of the general formula (Ic) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 7: A compound of the general formula (Ic) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 8: A compound of the general formula (Ic) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 9: A compound of the general formula (Ic) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 10: A compound of the general formula (Id) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 11: A compound of the general formula (Id) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 12: A compound of the general formula (Id) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 13: A compound of the general formula (Id) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 14: A compound of the general formula (Ie) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 15: A compound of the general formula (Ie) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 16: A compound of the general formula (Ie) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 17: A compound of the general formula (Ie) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 18: A compound of the general formula (If) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 19: A compound of the general formula (If) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 20: A compound of the general formula (If) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 21: A compound of the general formula (If) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 22: A compound of the general formula (Ig) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 23: A compound of the general formula (Ig) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 24: A compound of the general formula (Ig) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 25: A compound of the general formula (Ig) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 26: A compound of the general formula (Ih) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 27: A compound of the general formula (Ih) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 28: A compound of the general formula (Ih) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 29: A compound of the general formula (Ih) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 30: A compound of the general formula (Ii) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 31: A compound of the general formula (Ii) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 32: A compound of the general formula (Ii) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 33: A compound of the general formula (Ii) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 34: A compound of the general formula (Ik) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 35: A compound of the general formula (Ik) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 36: A compound of the general formula (Ik) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 37: A compound of the general formula (Ik) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 38: A compound of the general formula (Im) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 39: A compound of the general formula (Im) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 40: A compound of the general formula (Im) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 41: A compound of the general formula (Im) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 42: A compound of the general formula (In) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 43: A compound of the general formula (In) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 44: A compound of the general formula (In) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 45: A compound of the general formula (In) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 46: A compound of the general formula (Io) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 47: A compound of the general formula (Io) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 48: A compound of the general formula (Io) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 49: A compound of the general formula (Io) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 50: A compound of the general formula (Ip) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 51: A compound of the general formula (Ip) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 52: A compound of the general formula (Ip) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 53: A compound of the general formula (Ip) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 54: A compound of the general formula (Iq) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 55: A compound of the general formula (Iq) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 56: A compound of the general formula (Iq) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 57: A compound of the general formula (Iq) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 58: A compound of the general formula (Ir) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 59: A compound of the general formula (Ir) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 60: A compound of the general formula (Ir) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 61: A compound of the general formula (Ir) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 62: A compound of the general formula (Is) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 63: A compound of the general formula (Is) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 64: A compound of the general formula (Is) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 65: A compound of the general formula (Is) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 66: A compound of the general formula (It) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 67: A compound of the general formula (It) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 68: A compound of the general formula (It) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 69: A compound of the general formula (It) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 70: A compound of the general formula (Iu) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 71: A compound of the general formula (Iu) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 72: A compound of the general formula (Iu) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 73: A compound of the general formula (Iu) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 74: A compound of the general formula (Iv) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 75: A compound of the general formula (Iv) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 76: A compound of the general formula (Iv) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 77: A compound of the general formula (Iv) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 78: A compound of the general formula (Iw) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 79: A compound of the general formula (Iw) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 80: A compound of the general formula (Iw) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 81: A compound of the general formula (Iw) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 82: A compound of the general formula (Ix) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 83: A compound of the general formula (Ix) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 84: A compound of the general formula (Ix) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 85: A compound of the general formula (Ix) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 86: A compound of the general formula (Iy) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 87: A compound of the general formula (Iy) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 88: A compound of the general formula (Iy) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 89: A compound of the general formula (Iy) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 90: A compound of the general formula (Iz) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 91: A compound of the general formula (Iz) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 92: A compound of the general formula (Iz) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 93: A compound of the general formula (Iz) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 94: A compound of the general formula (Iz₁) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 95: A compound of the general formula (Iz₁) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 96: A compound of the general formula (Iz₁) wherein n is 4 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 97: A compound of the general formula (Iz₁) wherein n is 5 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 98: A compound of the general formula (Iz₂) wherein n is 2 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 99: A compound of the general formula (Iz₂) wherein n is 3 and thecombination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 100: A compound of the general formula (Iz₂) wherein n is 4 andthe combination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 101: A compound of the general formula (Iz₂) wherein n is 5 andthe combination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 102: A compound of the general formula (Iz₃) wherein n is 2 andthe combination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 103: A compound of the general formula (Iz₃) wherein n is 3 andthe combination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 104: A compound of the general formula (Iz₃) wherein n is 4 andthe combination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Table 105: A compound of the general formula (Iz₃) wherein n is 5 andthe combination of the substituents R₁₀, X₁ and X₂ for each compoundcorresponds to a line A.1 to A.268 of Table A.

Formulation Examples %=Percent by Weight

Example F1: Emulsifiable concentrates a) b) c) active ingredient 25% 40%50% calcium dodecylbenzenesulfonate  5%  8%  6% castor oil polyethyleneglycol ether (36 mol EO)  5% — — tributylphenol polyethylene glycolether — 12%  4% (30 mol EO) cyclohexanone — 15% 20% xylene mixture 65%25% 20%Mixing finely ground active ingredient and additives gives anemulsifiable concentrate which yields emulsions of the desiredconcentration on dilution with water.

Example F2: Solutions a) b) c) d) active ingredient 80% 10% 5% 95%ethylene glycol monomethyl ether 20% — — — polyethylene glycol (MW 400)— 70% — — N-methylpyrrolid-2-one — 20% — — epoxidised coconut oil — — 1% 5% benzine (boiling range: 160-190°) — — 94%  —Mixing finely ground active ingredient and additives gives a solutionsuitable for use in the form of microdrops.

Example F3: Granules a) b) c) d) active ingredient 5% 10%  8% 21% kaolin94%  — 79% 54% highly dispersed silicic acid 1% — 13%  7% attapulgite —90% — 18%The active ingredient is dissolved in dichloromethane, the solution issprayed onto the carrier mixture and the solvent is evaporated off invacuo.

Biological Examples Example B1 Action against Heliothis VirescensCaterpillars

Young soybean plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of test compound. After the spray-coating has dried,the soybean plants are populated with 10 caterpillars of Heliothisvirescens in the first stage and placed in a plastics container.Evaluation is made 6 days later. The percentage reduction in populationand the percentage reduction in feeding damage (% activity) aredetermined by comparing the number of dead caterpillars and the feedingdamage on the treated plants with that on the untreated plants.

The compounds of the Tables exhibit good activity against Heliothisvirescens in this test. In particular, the compounds 1.3, 1.4, 1.5, 1.10to 1.13, 1.16, 1.17, 1.19 and 1.21 are more than 80% effective.

Example B2 Action against Plutella Xylostella Caterpillars

Young cabbage plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of test compound. After the spray-coating has dried,the cabbage plants are populated with 10 caterpillars of Plutellaxylostella in the third stage and placed in a plastics container.Evaluation is made 3 days later. The percentage reduction in populationand the percentage reduction in feeding damage (% activity) aredetermined by comparing the number of dead caterpillars and the feedingdamage on the treated plants with that on the untreated plants.

The compounds of the Tables exhibit good activity against Plutellaxylostella. In particular, the compounds 1.3, 1.4, 1.5, 1.10 to 1.13,1.16, 1.17, 1.19 and 1.21 are more than 80% effective.

Example B3 Action against Spodoptera littoralis

Young soybean plants are sprayed with an aqueous emulsion spray mixturecomprising 400 ppm of test compound and, after the spray-coating hasdried, the plants are populated with 10 caterpillars of Spodopteralittoralis in the first stage and then placed in a plastics container. 3days later, the percentage reduction in population and the percentagereduction in feeding damage (% activity) are determined by comparing thenumber of dead caterpillars and the feeding damage on the treated plantswith that on untreated plants.

The compounds of the Tables exhibit good activity in this test. Inparticular, the compounds 1.3, 1.4, 1.5, 1.10 to 1.13, 1.16, 1.17, 1.19and 1.21 are more than 80% effective.

1. A compound of formula

wherein A₀, A₁ and A₂ are each independently of the other a bond or aC₁-C₆alkylene group which is unsubstituted or substituted by from one tosix identical or different substituents selected from C₃-C₈cycloalkyl,C₃-C₈cycloalkyl-C₁-C₆alkyl and C₁-C₃haloalkyl; A₃ is a C₁-C₆alkylenegroup which is unsubstituted or substituted by from one to six identicalor different substituents selected from C₃-C₈cycloalkyl,C₃-C₈cycloalkyl-C₁-C₆alkyl and C₁-C₃haloalkyl; D is CH; X₁ and X₂ areeach independently of the other fluorine, chlorine or bromine; R₁, R₂and R₃ are each independently of the others H, halogen, OH, SH, CN,nitro, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl, C₂-C₆alkenyl,C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy,—S(═O)—C₁-C₆alkyl, —S(O)₂—C₁-C₆alkyl, C₁-C₆alkoxycarbonyl orC₃-C₆haloalkynyloxy; the substituents R₃ being independent of oneanother when m is 2; R₄ is H, halogen, OH, SH, CN, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl, C₂-C₆-alkenyl, C₂-C₆haloalkenyl,C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy,C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy, —S(═O)—C₁-C₆alkyl,—S(═O)₂—C₁-C₆alkyl or C₁-C₆alkoxycarbonyl; the substituents R₄ beingindependent of one another when k is greater than 1; or N(R₅)₂ whereinthe two substituents R₅ are independent of one another; R₅ is H, CN, OH,C₁-C₆alkyl, C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₆alkyl, C₁-C₆haloalkyl,C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy,C₂-C₆alkynyloxy, —C(═O)R₈, —C(═S)R₈, phenyl, benzyl; or phenyl or benzyleach of which is substituted in the aromatic ring by from one to fiveidentical or different substituents selected from the group consistingof halogen, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy, halo-C₁-C₆-alkoxy,hydroxy, cyano and nitro; or the two substituents R₅ together form afour- to eight-membered, straight-chain or branched alkylene bridgewherein a CH₂ group may have been replaced by O, S or NR₉, and thealkylene bridge is unsubstituted or substituted by from one to fouridentical or different substituents selected from C₃-C₈cycloalkyl,C₃-C₈cycloalkyl-C₁-C₆alkyl and C₁-C₃haloalkyl; W is O, NR₆, S, SO, SO₂,—C(═O)—O—, —O—C(═O)—, —C(═O)—NR₇— or —NR₇—C(═O)—; T is a bond; Q is O,NR₆, S, SO or SO₂; Y is O, NR₆, S, SO or SO₂; R₆ and R₇ areindependently of each other H, C₁-C₆alkyl, C₁-C₃haloalkyl,C₁-C₆alkylcarbonyl, C₁-C₃haloalkylcarbonyl, C₁-C₆alkoxyalkyl,C₃-C₈cycloalkyl or benzyl; R₈ is C₁-C₆alkyl, C₁-C₆haloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₁-C₆alkoxy,C₁-C₆haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆haloalkenyloxy, C₂-C₆alkynyloxy,C₃-C₆cycloalkyl, phenyl, benzyl; or phenyl or benzyl each of which isunsubstituted or substituted by from one to three identical or differentsubstituents selected from halogen, CN, nitro, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,C₂-C₆alkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl,C₁-C₃haloalkoxycarbonyl and C₂-C₆haloalkenyloxy; R₉ is H, C₁-C₆alkyl,C₁-C₃haloalkyl, C₁-C₆-alkylcarbonyl, C₁-C₆haloalkylcarbonyl,C₁-C₆alkoxyalkyl, C₃-C₈cycloalkyl or benzyl; k is 1, 2, 3 or 4 when D isCH; m is 1 or 2; E is 1,2,4-oxadiazol-3-yl which is unsubstituted ormonosubstituted by CN, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl,C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₃-C₆alkynyl, C₃-C₆cycloalkyl,C₁-C₆alkylcarbonyl, C₁-C₆haloalkylcarbonyl or by C₁-C₆alkoxycarbonyl;and, where applicable, their possible E/Z isomers, E/Z isomeric mixturesand/or tautomers, in each case in free form or in salt form.
 2. Thecompound according to claim 1 of formula (I) in free form.
 3. Thecompound according to claim 1, of formula (I), wherein X₁ and X₂ arechlorine or bromine.
 4. A pesticidal composition which comprises asactive ingredient at least one compound according to claim 1 of formula(I), in free form or in agrochemically acceptable salt form, and atleast one adjuvant.
 5. A process for the preparation of a composition asdescribed in claim 4, which comprises mixing the active ingredient withthe adjuvant(s).
 6. A method of controlling pests, which comprisesapplying a pesticidal composition as described in claim 4 to the pestsor to the locus thereof.